Delivery of surfactant soluble anti-dandruff agent

ABSTRACT

A hair care composition directed to from about 14% to about 40% of one or more surfactants; from about 0.1% to 10% of one or more surfactant soluble antidandruff agents; wherein when the hair care composition is diluted to 1.3% surfactant concentration has a ratio of surfactant diffusion coefficient to soluble agent diffusion coefficient less than 0.6 or greater than 1.4.

FIELD OF THE INVENTION

The present invention is directed to delivery of a surfactant solublescalp agent from a hair care composition.

BACKGROUND OF THE INVENTION

For years, anti-dandruff shampoos have been widely used to treatdandruff and clean hair and scalp, but there still remains a need forimproved anti-dandruff shampoos. In general, anti-dandruff shampoos areformulated with anti-dandruff agents in combination with surfactants andaqueous systems that are intended to deposit the anti-dandruff agents onthe scalp. The anti-dandruff agents can be insoluble particulates suchas zinc pyrithione and/or surfactant soluble substances such asclimbazole or octopirox. Many anti-dandruff shampoos use cationicpolymers with anionic surfactants to form coacervate which aid in thedeposition of insoluble particulate agents. However, generallycoacervates do not impact soluble agents deposition as the solubleagents do not associate with the coacervates formed between the cationicpolymers and anionic surfactants. Indeed it can prove difficult todeposit on scalp much more than 1-2% of the soluble agents present inanti-dandruff shampoos while the remaining 98-99% of the soluble agentsin the formulas are rinsed away. As many of the anti-dandruff agents canbe relatively expensive, allowing >97% of the soluble agents to rinseaway is equivalent to pouring money down the drain, and so there remainsa need for a shampoo that can more efficiently deposit solubleanti-dandruff agents. Also, as consumers continue to desire a shampoothat delivers superior anti-dandruff efficacy and lower agent depositionresults in lower anti-dandruff efficacy, there remains a need for ashampoo that can deposit on scalp a higher percentage of the solubleagents present in anti-dandruff shampoos.

The association of many classes of surfactants into micellar aggregatesis a well-known phenomenon. Micelles are often drawn as staticstructures of spherical aggregates, but in truth micelles are in dynamicequilibrium with individual surfactant molecules (monomers) that areconstantly being exchanged between the bulk and the micelles.Additionally, the micelles themselves are continuously disintegratingand reassembling. There are two relaxation processes involved inmicellar solutions. The first is a fast relaxation process referred toas τ₁, which is associated with the quick exchange of monomers betweenmicelles and the surrounding bulk phase. The second relaxation time, τ₂,is attributed to the micelle formation and dissolution process (i.e.,the lifetime of the micelle). Extensive experimental research on thekinetics of micellization by Shah and co-workers (Patist, A., Jha, B.K., Oh, S. G., and Shah, D. O., J. Surfactants Deterg. 2, 317, (1999);James-Smith, M. A., Shekhawat, D., and Shah, D. O., Tenside Surf Det.44, 142 (2007)) showed a strong correlation of τ₂ with a number ofdetergency properties including oil solubilization in micellar solutionsand droplet size in emulsions, as well as surfactant properties such asdynamic surface tension and micelle stability. Their research alsoshowed a strong inverse correlation of τ₂ with other properties such asfoamability and concentration of sub-micellar aggregates. Specifically,they showed that a maximal τ₂ and thus maximal micellar stabilitycorresponded to both a maximal rate of oil solubilization and maximalamount of oil solubilized. Logic would therefore suggest that acleansing composition with longer τ₂, more stable micelles, and fasterrate of solubilization would be preferred since such a system can cleanbetter, more quickly solubilize larger quantities of oils orsurfactant-soluble materials and should be more stable. Surprisinglyhowever, it has been found that a composition with a surfactant systemof shorter τ₂, less stable micelles, and a slower rate ofsolubilization, as demonstrated in FIG. 1, is preferred.

SUMMARY OF THE INVENTION

In an embodiment of the present invention, it is directed to a hair carecomposition comprising from about 14% to about 40% of one or moresurfactants; from about 0.1% to 10% of one or more surfactant solubleantidandruff agents; wherein when the hair care composition is dilutedto 1.3% surfactant concentration has a ratio of surfactant diffusioncoefficient to soluble agent diffusion coefficient less than 0.6 orgreater than 1.4.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of the rate of octopirox solubilization as a functionof surfactant composition.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

All percentages and ratios used herein are by weight of the totalcomposition, unless otherwise designated. All measurements areunderstood to be made at ambient conditions, where “ambient conditions”means conditions at about 25° C., under about one atmosphere ofpressure, and at about 50% relative humidity, unless otherwisedesignated. All numeric ranges are inclusive of narrower ranges;delineated upper and lower range limits are combinable to create furtherranges not explicitly delineated.

The compositions of the present invention can comprise, consistessentially of, or consist of, the essential components as well asoptional ingredients described herein. As used herein, “consistingessentially of” means that the composition or component may includeadditional ingredients, but only if the additional ingredients do notmaterially alter the basic and novel characteristics of the claimedcompositions or methods.

“Apply” or “application,” as used in reference to a composition, meansto apply or spread the compositions of the present invention ontokeratinous tissue such as the hair.

“Dermatologically acceptable” means that the compositions or componentsdescribed are suitable for use in contact with human skin tissue withoutundue toxicity, incompatibility, instability, allergic response, and thelike.

“Safe and effective amount” means an amount of a compound or compositionsufficient to significantly induce a positive benefit.

While the specification concludes with claims particularly pointing outand distinctly claiming the invention, it is believed that the presentinvention will be better understood from the following description.

As used herein, the term “fluid” includes liquids and gels.

As used herein, the articles including “a” and “an” when used in aclaim, are understood to mean one or more of what is claimed ordescribed.

As used herein, “comprising” means that other steps and otheringredients which do not affect the end result can be added. This termencompasses the terms “consisting of” and “consisting essentially of”.

As used herein, “mixtures” is meant to include a simple combination ofmaterials and any compounds that may result from their combination.

As used herein, “molecular weight” or “Molecular weight” refers to theweight average molecular weight unless otherwise stated. Molecularweight is measured using industry standard method, gel permeationchromatography (“GPC”).

Where amount ranges are given, these are to be understood as being thetotal amount of said ingredient in the composition, or where more thanone species fall within the scope of the ingredient definition, thetotal amount of all ingredients fitting that definition, in thecomposition.

For example, if the composition comprises from 1% to 5% fatty alcohol,then a composition comprising 2% stearyl alcohol and 1% cetyl alcoholand no other fatty alcohol, would fall within this scope.

The amount of each particular ingredient or mixtures thereof describedhereinafter can account for up to 100% (or 100%) of the total amount ofthe ingredient(s) in the hair care composition.

As used herein, “personal care compositions” includes products such asshampoos, shower gels, liquid hand cleansers, hair colorants, facialcleansers, and other surfactant-based liquid compositions

As used herein, the terms “include,” “includes,” and “including,” aremeant to be non-limiting and are understood to mean “comprise,”“comprises,” and “comprising,” respectively.

All percentages, parts and ratios are based upon the total weight of thecompositions of the present invention, unless otherwise specified. Allsuch weights as they pertain to listed ingredients are based on theactive level and, therefore, do not include carriers or by-products thatmay be included in commercially available materials.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

While the τ₂ and micelle stability of a surfactant system and thesolubility of surfactant-soluble agents in that system are important, ofequal importance are the surfactant micelle stability and solubility andrate of solubilization of the agents in the system after dilution, suchas when the cleansing composition is applied to the head during use. Oneway of understanding the solubility and associations of the solubleagent in the surfactant system upon dilution is to measure by NMR thediffusion coefficients of the surfactant and the surfactant-solubleagents in a diluted sample. If the diffusion coefficients of thesurfactant and the agent are similar such that the ratio of the twocoefficients is close to 1.0, one is able to infer that thesurfactant-soluble agent is within or closely associated with thesurfactant micelles. However if the diffusion coefficients of thesurfactant and the agent are very different such that the ratio of thetwo coefficients is significantly more or less than 1.0, then one isable to infer that the surfactant-soluble agent is not within orassociated with the surfactant micelles. This in turn implies that thesurfactant-soluble agent is less soluble in the diluted surfactant ofthe latter case.

It has been found that a soluble anti-dandruff agent containingcleansing composition, which when diluted to 1.3% surfactantconcentration has a ratio of surfactant diffusion coefficient to solubleagent diffusion coefficient less than 0.8 or greater than 1.2, candeposit that soluble agent with ˜1.4× or greater efficiency than asoluble anti-dandruff agent containing composition whose ratio ofdiffusion coefficients is close to 1.0.

Without being bound by theory, the increased deposition efficiencyexhibited by embodiments of the present invention can surprisingly befurther increased by additionally incorporating an oil which phaseseparates upon dilution in combination with a cationic polymer whichforms coacervate upon dilution. The coacervate aids in the deposition ofthe oil within which the surfactant-soluble agent should be at leastpartially soluble, thus resulting in an incremental increase in thetotal percentage of soluble agent deposited.

Surfactant-soluble agents are defined as materials which are insolublein water but soluble at a concentration of 0.1% or higher in an aqueoussolution of 10% sodium laureth-1 sulfate. A conventional method may beused to determine solubility. Such method may include wherein solubilityof a material of interest can be determined by first visually assessingthat the material containing sodium laureth-1 sulfate mixture ishomogeneous, followed by filling a glass jar with the materialcontaining sodium laureth-1 sulfate mixture, then placing a Class 2standard red laser pointer such as the Quartet Class 2 standard laserpointer (model MP-1202Q) against the side of the jar and shining thelaser through the jar. If the material is soluble in the sodiumlaureth-1 solution the laser light will not be scattered, resulting inonly an observable red dot appearing on the side of the jar opposite thelaser pointer and no visible red laser beam will be observed passingthrough the solution.

Soluble Anti-Dandruff Agent

Anti-dandruff agent may be one material or a mixture selected from thegroups consisting of: azoles, such as climbazole, ketoconazole,itraconazole, econazole, and elubiol; hydroxy pyridones, such asoctopirox (piroctone olamine), ciclopirox, rilopirox, andMEA-Hydroxyoctyloxypyridinone; kerolytic agents, such as salicylic acidand other hydroxy acids; strobilurins such as azoxystrobin and metalchelators such as 1,10-phenanthroline.

In an embodiment, the azole anti-microbials is an imidazole selectedfrom the group consisting of: benzimidazole, benzothiazole, bifonazole,butaconazole nitrate, climbazole, clotrimazole, croconazole,eberconazole, econazole, elubiol, fenticonazole, fluconazole,flutimazole, isoconazole, ketoconazole, lanoconazole, metronidazole,miconazole, neticonazole, omoconazole, oxiconazole nitrate,sertaconazole, sulconazole nitrate, tioconazole, thiazole, and mixturesthereof, or the azole anti-microbials is a triazole selected from thegroup consisting of: terconazole, itraconazole, and mixtures thereof. Inan embodiment, the azole anti-microbial agent is ketoconazole. In anembodiment, the sole anti-microbial agent is ketoconazole.

In an embodiment, the soluble anti-dandruff agent may be present in anamount from about 0.1% to 10%, in a further embodiment from about 0.25%to 8%, in yet a further embodiment from about 0.5% to 6%.

A. Detersive Surfactant

The hair care composition may comprise greater than about 14% by weightof a surfactant system which provides cleaning performance to thecomposition, in an embodiment greater than 20% by weight of a surfactantsystem which provides cleaning performance to the composition. Thesurfactant system comprises an anionic surfactant and/or a combinationof anionic surfactants and/or a combination of anionic surfactants andco-surfactants selected from the group consisting of amphoteric,zwitterionic, nonionic and mixtures thereof. Various examples anddescriptions of detersive surfactants are set forth in U.S. Pat. No.8,440,605; U.S. Patent Application Publication No. 2009/155383; and U.S.Patent Application Publication No. 2009/0221463, which are incorporatedherein by reference in their entirety.

In an embodiment, the hair care composition may comprise from about 14%to about 40%, from about 15% to about 36%, from about 18% to about 32%,and/or from about 20% to about 28% by weight of one or more surfactants.

Anionic surfactants suitable for use in the compositions are the alkyland alkyl ether sulfates. Other suitable anionic surfactants are thewater-soluble salts of organic, sulfuric acid reaction products. Stillother suitable anionic surfactants are the reaction products of fattyacids esterified with isethionic acid and neutralized with sodiumhydroxide. Other similar anionic surfactants are described in U.S. Pat.Nos. 2,486,921; 2,486,922; and 2,396,278, which are incorporated hereinby reference in their entirety.

Exemplary anionic surfactants for use in the hair care compositioninclude ammonium lauryl sulfate, ammonium laureth sulfate, ammoniumC10-15 pareth sulfate, ammonium C10-15 alkyl sulfate, ammonium C11-15alkyl sulfate, ammonium decyl sulfate, ammonium deceth sulfate, ammoniumundecyl sulfate, ammonium undeceth sulfate, triethylamine laurylsulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate,triethanolamine laureth sulfate, monoethanolamine lauryl sulfate,monoethanolamine laureth sulfate, diethanolamine lauryl sulfate,diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate,sodium lauryl sulfate, sodium laureth sulfate, sodium C10-15 parethsulfate, sodium C10-15 alkyl sulfate, sodium C11-15 alkyl sulfate,sodium decyl sulfate, sodium deceth sulfate, sodium undecyl sulfate,sodium undeceth sulfate, potassium lauryl sulfate, potassium laurethsulfate, potassium C10-15 pareth sulfate, potassium C10-15 alkylsulfate, potassium C11-15 alkyl sulfate, potassium decyl sulfate,potassium deceth sulfate, potassium undecyl sulfate, potassium undecethsulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, laurylsarcosine, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroylsulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoylsulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate,triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate,monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate,sodium dodecyl benzene sulfonate, sodium cocoyl isethionate andcombinations thereof. In a further embodiment, the anionic surfactant issodium lauryl sulfate or sodium laureth sulfate.

The composition of the present invention can also include anionicsurfactants selected from the group consisting of:

a) R₁O(CH₂CHR₃O)_(y)SO₃M;

b) CH₃(CH₂)_(z)CHR₂CH₂O(CH₂CHR₃O)_(y)SO₃M; and

c) mixtures thereof,

where R₁ represents CH₃(CH₂)₁₀, R₂ represents H or a hydrocarbon radicalcomprising 1 to 4 carbon atoms such that the sum of the carbon atoms inz and R₂ is 8, R₃ is H or CH₃, y is 0 to 7, the average value of y isabout 1 when y is not zero (0), and M is a monovalent or divalent,positively-charged cation.

Suitable anionic alkyl sulfates and alkyl ether sulfate surfactantsinclude, but are not limited to, those having branched alkyl chainswhich are synthesized from C8 to C18 branched alcohols which may beselected from the group consisting of: Guerbet alcohols, aldolcondensation derived alcohols, oxo alcohols and mixtures thereof.Non-limiting examples of the 2-alkyl branched alcohols include oxoalcohols such as 2-methyl-1-undecanol, 2-ethyl-1-decanol,2-propyl-1-nonanol, 2-butyl 1-octanol, 2-methyl-1-dodecanol,2-ethyl-1-undecanol, 2-propyl-1-decanol, 2-butyl-1-nonanol,2-pentyl-1-octanol, 2-pentyl-1-heptanol, and those sold under thetradenames LIAL® (Sasol), ISALCHEM® (Sasol), and NEODOL® (Shell), andGuerbet and aldol condensation derived alcohols such as2-ethyl-1-hexanol, 2-propyl-1-butanol, 2-butyl-1-octanol,2-butyl-1-decanol, 2-pentyl-1-nonanol, 2-hexyl-1-octanol,2-hexyl-1-decanol and those sold under the tradename ISOFOL® (Sasol) orsold as alcohol ethoxylates and alkoxylates under the tradenamesLUTENSOL XP® (BASF) and LUTENSOL XL® (BASF).

The anionic alkyl sulfates and alkyl ether sulfates may also includethose synthesized from C8 to C18 branched alcohols derived from butyleneor propylene which are sold under the trade names EXXAL™ (Exxon) andMarlipal® (Sasol). This includes anionic surfactants of the subclass ofsodium trideceth-n sulfates (STnS), where n is between about 0.5 andabout 3.5. Exemplary surfactants of this subclass are sodium trideceth-2sulfate and sodium trideceth-3 sulfate. The composition of the presentinvention can also include sodium tridecyl sulfate.

The composition of the present invention can also include anionic alkyland alkyl ether sulfosuccinates and/or dialkyl and dialkyl ethersulfosuccinates and mixtures thereof. The dialkyl and dialkyl ethersulfosuccinates may be a C6-15 linear or branched dialkyl or dialkylether sulfosuccinate. The alkyl moieties may be symmetrical (i.e., thesame alkyl moieties) or asymmetrical (i.e., different alkyl moieties).Nonlimiting examples include: disodium lauryl sulfosuccinate, disodiumlaureth sulfosuccinate, sodium bistridecyl sulfosuccinate, sodiumdioctyl sulfosuccinate, sodium dihexyl sulfosuccinate, sodiumdicyclohexyl sulfosuccinate, sodium diamyl sulfosuccinate, sodiumdiisobutyl sulfosuccinate, linear bis(tridecyl) sulfosuccinate andmixtures thereof.

The hair care composition may comprise a co-surfactant. Theco-surfactant can be selected from the group consisting of amphotericsurfactant, zwitterionic surfactant, non-ionic surfactant and mixturesthereof. The co-surfactant can include, but is not limited to,lauramidopropyl betaine, cocoamidopropyl betaine, laurylhydroxysultaine, sodium lauroamphoacetate, disodium cocoamphodiacetate,cocamide monoethanolamide and mixtures thereof.

The hair care composition may further comprise from about 0.25% to about15%, from about 2% to about 14%, from about 3% to about 13% by weight ofone or more amphoteric, zwitterionic, nonionic co-surfactants, or amixture thereof.

Suitable amphoteric or zwitterionic surfactants for use in the hair carecomposition herein include those which are known for use in shampoo orother hair care cleansing. Non limiting examples of suitablezwitterionic or amphoteric surfactants are described in U.S. Pat. Nos.5,104,646 and 5,106,609, which are incorporated herein by reference intheir entirety.

Amphoteric co-surfactants suitable for use in the composition includethose surfactants described as derivatives of aliphatic secondary andtertiary amines in which the aliphatic radical can be straight orbranched chain and wherein one of the aliphatic substituents containsfrom about 8 to about 18 carbon atoms and one contains an anionic groupsuch as carboxy, sulfonate, sulfate, phosphate, or phosphonate. Suitableamphoteric surfactant include, but are not limited to, thoseselectedfrom the group consisting of: sodium cocaminopropionate, sodiumcocaminodipropionate, sodium cocoamphoacetate, sodiumcocoamphodiacetate, sodium cocoamphohydroxypropylsulfonate, sodiumcocoamphopropionate, sodium cornamphopropionate, sodiumlauraminopropionate, sodium lauroamphoacetate, sodiumlauroamphodiacetate, sodium lauroamphohydroxypropylsulfonate, sodiumlauroamphopropionate, sodium cornamphopropionate, sodiumlauriminodipropionate, ammonium cocaminopropionate, ammoniumcocaminodipropionate, ammonium cocoamphoacetate, ammoniumcocoamphodiacetate, ammonium cocoamphohydroxypropylsulfonate, ammoniumcocoamphopropionate, ammonium cornamphopropionate, ammoniumlauraminopropionate, ammonium lauroamphoacetate, ammoniumlauroamphodiacetate, ammonium lauroamphohydroxypropylsulfonate, ammoniumlauroamphopropionate, ammonium cornamphopropionate, ammoniumlauriminodipropionate, triethanolamine cocaminopropionate,triethanolamine cocaminodipropionate, triethanolamine cocoamphoacetate,triethanolamine cocoamphohydroxypropylsulfonate, triethanolaminecocoamphopropionate, triethanolamine cornamphopropionate,triethanolamine lauraminopropionate, triethanolamine lauroamphoacetate,triethanolamine lauroamphohydroxypropylsulfonate, triethanolaminelauroamphopropionate, triethanolamine cornamphopropionate,triethanolamine lauriminodipropionate, cocoamphodipropionic acid,disodium caproamphodiacetate, disodium caproamphoadipropionate, disodiumcapryloamphodiacetate, disodium capryloamphodipriopionate, disodiumcocoamphocarboxyethylhydroxypropylsulfonate, disodiumcocoamphodiacetate, disodium cocoamphodipropionate, disodiumdicarboxyethylcocopropylenediamine, disodium laureth-5carboxyamphodiacetate, disodium lauriminodipropionate, disodiumlauroamphodiacetate, disodium lauroamphodipropionate, disodiumoleoamphodipropionate, disodium PPG-2-isodecethyl-7carboxyamphodiacetate, lauraminopropionic acid, lauroamphodipropionicacid, lauryl aminopropylglycine, lauryl diethylenediaminoglycine, andmixtures thereof

The composition may comprises a zwitterionic co-surfactant, wherein thezwitterionic surfactant is a derivative of aliphatic quaternaryammonium, phosphonium, and sulfonium compounds, in which the aliphaticradicals can be straight or branched chain, and wherein one of thealiphatic substituents contains from about 8 to about 18 carbon atomsand one contains an anionic group such as carboxy, sulfonate, sulfate,phosphate or phosphonate. The zwitterionic surfactant can be selectedfrom the group consisting of: cocamidoethyl betaine, cocamidopropylamineoxide, cocamidopropyl betaine, cocamidopropyl dimethylaminohydroxypropylhydrolyzed collagen, cocamidopropyldimonium hydroxypropyl hydrolyzedcollagen, cocamidopropyl hydroxysultaine, cocobetaineamidoamphopropionate, coco-betaine, coco-hydroxysultaine, coco/oleamidopropylbetaine, coco-sultaine, lauramidopropyl betaine, lauryl betaine, laurylhydroxysultaine, lauryl sultaine, and mixtures thereof.

Suitable nonionic surfactants for use in the present invention includethose described in McCutcheion's Detergents and Emulsifiers, NorthAmerican edition (1986), Allured Publishing Corp., and McCutcheion'sFunctional Materials, North American edition (1992). Suitable nonionicsurfactants for use in the personal care compositions of the presentinvention include, but are not limited to, polyoxyethylenated alkylphenols, polyoxyethylenated alcohols, polyoxyethylenatedpolyoxypropylene glycols, glyceryl esters of alkanoic acids,polyglyceryl esters of alkanoic acids, propylene glycol esters ofalkanoic acids, sorbitol esters of alkanoic acids, polyoxyethylenatedsorbitor esters of alkanoic acids, polyoxyethylene glycol esters ofalkanoic acids, polyoxyethylenated alkanoic acids, alkanolamides,N-alkylpyrrolidones, alkyl glycosides, alkyl polyglucosides, alkylamineoxides, and polyoxyethylenated silicones.

The co-surfactant can be a non-ionic surfactant selected from thealkanolamides group including: Cocamide, Cocamide Methyl MEA, CocamideDEA, Cocamide MEA, Cocamide MIPA, Lauramide DEA, Lauramide MEA,Lauramide MIPA, Myristamide DEA, Myristamide MEA, PEG-20 Cocamide MEA,PEG-2 Cocamide, PEG-3 Cocamide, PEG-4 Cocamide, PEG-5 Cocamide, PEG-6Cocamide, PEG-7 Cocamide, PEG-3 Lauramide, PEG-5 Lauramide, PEG-3Oleamide, PPG-2 Cocamide, PPG-2 Hydroxyethyl Cocamide, PPG-2Hydroxyethyl Isostearamide and mixtures thereof.

Representative polyoxyethylenated alcohols include alkyl chains rangingin the C9-C16 range and having from about 1 to about 110 alkoxy groupsincluding, but not limited to, laureth-3, laureth-23, ceteth-10,steareth-10, steareth-100, beheneth-10, and commercially available fromShell Chemicals, Houston, Tex. under the trade names Neodol® 91, Neodol®23, Neodol® 25, Neodol® 45, Neodol® 135, Neodo®1 67, Neodol® PC 100,Neodol® PC 200, Neodol® PC 600, and mixtures thereof.

Also available commercially are the polyoxyethylene fatty ethersavailable commercially under the Brij® trade name from Uniqema,Wilmington, Del., including, but not limited to, Brij® 30, Brij® 35,Brij® 52, Brij® 56, Brij® 58, Brij® 72, Brij® 76, Brij® 78, Brij® 93,Brij® 97, Brij® 98, Brij® 721 and mixtures thereof.

Suitable alkyl glycosides and alkyl polyglucosides can be represented bythe formula (S)n-O—R wherein S is a sugar moiety such as glucose,fructose, mannose, galactose, and the like; n is an integer of fromabout 1 to about 1000, and R is a C8-C30 alkyl group. Examples of longchain alcohols from which the alkyl group can be derived include decylalcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearylalcohol, oleyl alcohol, and the like. Examples of these surfactantsinclude alkyl polyglucosides wherein S is a glucose moiety, R is a C8-20alkyl group, and n is an integer of from about 1 to about 9.Commercially available examples of these surfactants include decylpolyglucoside and lauryl polyglucoside available under trade names APG®325 CS, APG® 600 CS and APG® 625 CS) from Cognis, Ambler, Pa. Alsouseful herein are sucrose ester surfactants such as sucrose cocoate andsucrose laurate and alkyl polyglucosides available under trade namesTriton™ BG-10 and Triton™ CG-110 from The Dow Chemical Company, Houston,Tx.

Other nonionic surfactants suitable for use in the present invention areglyceryl esters and polyglyceryl esters, including but not limited to,glyceryl monoesters, glyceryl monoesters of C12-22 saturated,unsaturated and branched chain fatty acids such as glyceryl oleate,glyceryl monostearate, glyceryl monopalmitate, glyceryl monobehenate,and mixtures thereof, and polyglyceryl esters of C12-22 saturated,unsaturated and branched chain fatty acids, such as polyglyceryl-4isostearate, polyglyceryl-3 oleate, polyglyceryl-2-sesquioleate,triglyceryl diisostearate, diglyceryl monooleate, tetraglycerylmonooleate, and mixtures thereof.

Also useful herein as nonionic surfactants are sorbitan esters. Sorbitanesters of C12-22 saturated, unsaturated, and branched chain fatty acidsare useful herein. These sorbitan esters usually comprise mixtures ofmono-, di-, tri-, etc. esters. Representative examples of suitablesorbitan esters include sorbitan monolaurate (SPAN® 20), sorbitanmonopalmitate (SPAN® 40), sorbitan monostearate (SPAN® 60), sorbitantristearate (SPAN® 65), sorbitan monooleate (SPAN® 80), sorbitantrioleate (SPAN® 85), and sorbitan isostearate.

Also suitable for use herein are alkoxylated derivatives of sorbitanesters including, but not limited to, polyoxyethylene (20) sorbitanmonolaurate (Tween® 20), polyoxyethylene (20) sorbitan monopalmitate(Tween® 40), polyoxyethylene (20) sorbitan mono stearate (Tween® 60),polyoxyethylene (20) sorbitan monooleate (Tween® 80), polyoxyethylene(4) sorbitan monolaurate (Tween® 21), polyoxyethylene (4) sorbitanmonostearate (Tween® 61), polyoxyethylene (5) sorbitan monooleate(Tween® 81), and mixtures thereof, all available from Uniqema.

Also suitable for use herein are alkylphenol ethoxylates including, butnot limited to, nonylphenol ethoxylates (Tergitol™ NP-4, NP-6, NP-7,NP-8, NP-9, NP-10, NP-11, NP-12, NP-13, NP-15, NP-30, NP-40, NP-50,NP-55, NP-70 available from The Dow Chemical Company, Houston, Tex.) andoctylphenol ethoxylates (Triton™ X-15, X-35, X-45, X-114, X-100, X-102,X-165, X-305, X-405, X-705 available from The Dow Chemical Company,Houston, Tx).

Also suitable for use herein are tertiary alkylamine oxides includinglauramine oxide and cocamine oxide.

Non limiting examples of other anionic, zwitterionic, amphoteric, andnon-ionic additional surfactants suitable for use in the hair carecomposition are described in McCutcheon's, Emulsifiers and Detergents,1989 Annual, published by M. C. Publishing Co., and U.S. Pat. Nos.3,929,678, 2,658,072; 2,438,091; 2,528,378, which are incorporatedherein by reference in their entirety.

Suitable surfactant combinations comprise an average weight % of alkylbranching of from about 0.5% to about 30%, alternatively from about 1%to about 25%, alternatively from about 2% to about 20%. The surfactantcombination can have a cumulative average weight % of C8 to C12 alkylchain lengths of from about 7.5% to about 25%, alternatively from about10% to about 22.5%, alternatively from about 10% to about 20%. Thesurfactant combination can have an average C8-C12/C13-C18 alkyl chainratio from about 3 to about 200, alternatively from about 25 to about175.5, alternatively from about 50 to about 150, alternatively fromabout 75 to about 125.

B. Cationic Polymers

The hair care composition also comprises a cationic polymer. Thesecationic polymers can include at least one of (a) a cationic guarpolymer, (b) a cationic non-guar galactomannan polymer, (c) a cationictapioca polymer, (d) a cationic copolymer of acrylamide monomers andcationic monomers, and/or (e) a synthetic, non-crosslinked, cationicpolymer, which may or may not form lyotropic liquid crystals uponcombination with the detersive surfactant (f) a cationic cellulosepolymer. Additionally, the cationic polymer can be a mixture of cationicpolymers.

The hair care composition may comprise a cationic guar polymer, which isa cationically substituted galactomannan (guar) gum derivatives. Guargum for use in preparing these guar gum derivatives is typicallyobtained as a naturally occurring material from the seeds of the guarplant. The guar molecule itself is a straight chain mannan, which isbranched at regular intervals with single membered galactose units onalternative mannose units. The mannose units are linked to each other bymeans of β(1-4) glycosidic linkages. The galactose branching arises byway of an α(1-6) linkage. Cationic derivatives of the guar gums areobtained by reaction between the hydroxyl groups of thepolygalactomannan and reactive quaternary ammonium compounds. The degreeof substitution of the cationic groups onto the guar structure should besufficient to provide the requisite cationic charge density describedabove.

According to one embodiment, the cationic polymer, including but notlimited to a cationic guar polymer, has a weight average Molecularweight of less than 1.5 million g/mol, or from about 150 thousand toabout 1.5 million g/mol, or from about 200 thousand to about 1.5 milliong/mol, or from about 300 thousand to about 1.2 million g/mol, or fromabout 750,000 thousand to about 1 million g/mol. In one embodiment, thecationic guar polymer has a charge density of from about 0.2 to about2.2 meq/g, or from about 0.3 to about 2.0 meq/g, or from about 0.4 toabout 1.8 meq/g; or from about 0.5 meq/g to about 1.7 meq/g.

According to one embodiment, the cationic guar polymer has a weightaverage Molecular weight of less than about 1.5 million g/mol, and has acharge density of from about 0.1 meq/g to about 2.5 meq/g. In anembodiment, the cationic guar polymer has a weight average molecularweight of less than 900 thousand g/mol, or from about 150 thousand toabout 800 thousand g/mol, or from about 200 thousand to about 700thousand g/mol, or from about 300 thousand to about 700 thousand g/mol,or from about 400 thousand to about 600 thousand g/mol. from about 150thousand to about 800 thousand g/mol, or from about 200 thousand toabout 700 thousand g/mol, or from about 300 thousand to about 700thousand g/mol, or from about 400 thousand to about 600 thousand g/mol.In one embodiment, the cationic guar polymer has a charge density offrom about 0.2 to about 2.2 meq/g, or from about 0.3 to about 2.0 meq/g,or from about 0.4 to about 1.8 meq/g; or from about 0.5 meq/g to about1.5 meq/g.

The hair care composition can comprise from about 0.05% to less thanabout 1%, from about 0.05% to about 0.9%, from about 0.1% to about 0.8%,or from about 0.2% to about 0.7% of cationic polymer (a), by totalweight of the composition.

The cationic guar polymer may be formed from quaternary ammoniumcompounds. In an embodiment, the quaternary ammonium compounds forforming the cationic guar polymer conform to the general formula 1:

wherein where R³, R⁴ and R⁵ are methyl or ethyl groups; R⁶ is either anepoxyalkyl group of the general formula 2:

or R⁶ is a halohydrin group of the general formula 3:

wherein R⁷ is a C₁ to C₃ alkylene; X is chlorine or bromine, and Z is ananion such as Cl—, Br—, I— or HSO₄—.

In an embodiment, the cationic guar polymer conforms to the generalformula 4:

wherein R⁸ is guar gum; and wherein R⁴, R⁵, R⁶ and R⁷ are as definedabove; and wherein Z is a halogen. In an embodiment, the cationic guarpolymer conforms to Formula 5:

Suitable cationic guar polymers include cationic guar gum derivatives,such as guar hydroxypropyltrimonium chloride. In an embodiment, thecationic guar polymer is a guar hydroxypropyltrimonium chloride.Specific examples of guar hydroxypropyltrimonium chlorides include theJaguar® series commercially available from Solvay, for example Jaguar®C-500, commercially available from Solvay. Jaguar® C-500 has a chargedensity of 0.8 meq/g and a molecular weight of 500,000 g/mol. Othersuitable guar hydroxypropyltrimonium chloride are: guarhydroxypropyltrimonium chloride which has a charge density of about 1.1meq/g and a molecular weight of about 500,000 g/mol is available fromASI, a charge density of about 1.5 meq/g and a molecular weight of about500,000 g/mole is available from ASI. Other suitable guarhydroxypropyltrimonium chloride are: Hi-Care 1000, which has a chargedensity of about 0.7 meq/g and a Molecular weight of about 600,000g/mole and is available from Solvay; N-Hance 3269 and N-Hance 3270,which have a charge density of about 0.7 meq/g and a molecular weight ofabout 425,000 g/mol and are available from ASI; N-Hance 3196, which hasa charge density of about 0.8 meq/g and a molecular weight of about1,100,000 g/mol and is available from ASI. AquaCat CG518 has a chargedensity of about 0.9 meq/g and a Molecular weight of about 50,000 g/moland is available from ASI. BF-13, which is a borate (boron) free guar ofcharge density of about 1.1 meq/g and molecular weight of about 800,000and BF-17, which is a borate (boron) free guar of charge density ofabout 1.7 meq/g and M. Wt. of about 800,000 both available from ASI.

The hair care compositions of the present invention may comprise agalactomannan polymer derivative having a mannose to galactose ratio ofgreater than 2:1 on a monomer to monomer basis, the galactomannanpolymer derivative selected from the group consisting of a cationicgalactomannan polymer derivative and an amphoteric galactomannan polymerderivative having a net positive charge. As used herein, the term“cationic galactomannan” refers to a galactomannan polymer to which acationic group is added. The term “amphoteric galactomannan” refers to agalactomannan polymer to which a cationic group and an anionic group areadded such that the polymer has a net positive charge.

Galactomannan polymers are present in the endosperm of seeds of theLeguminosae family. Galactomannan polymers are made up of a combinationof mannose monomers and galactose monomers. The galactomannan moleculeis a straight chain mannan branched at regular intervals with singlemembered galactose units on specific mannose units. The mannose unitsare linked to each other by means of β (1-4) glycosidic linkages. Thegalactose branching arises by way of an α (1-6) linkage. The ratio ofmannose monomers to galactose monomers varies according to the speciesof the plant and also is affected by climate. Non Guar Galactomannanpolymer derivatives of the present invention have a ratio of mannose togalactose of greater than 2:1 on a monomer to monomer basis. Suitableratios of mannose to galactose can be greater than about 3:1, and theratio of mannose to galactose can be greater than about 4:1. Analysis ofmannose to galactose ratios is well known in the art and is typicallybased on the measurement of the galactose content.

The gum for use in preparing the non-guar galactomannan polymerderivatives is typically obtained as naturally occurring material suchas seeds or beans from plants. Examples of various non-guargalactomannan polymers include but are not limited to Tara gum (3 partsmannose/1 part galactose), Locust bean or Carob (4 parts mannose/1 partgalactose), and Cassia gum (5 parts mannose/1 part galactose).

In one embodiment of the invention, the non-guar galactomannan polymerderivatives have a M. Wt. from about 1,000 to about 10,000,000, and/orfrom about 5,000 to about 3,000,000.

The hair care compositions of the invention can also includegalactomannan polymer derivatives which have a cationic charge densityfrom about 0.5 meq/g to about 7 meq/g. In one embodiment of the presentinvention, the galactomannan polymer derivatives have a cationic chargedensity from about 1 meq/g to about 5 meq/g. The degree of substitutionof the cationic groups onto the galactomannan structure should besufficient to provide the requisite cationic charge density.

The galactomannan polymer derivative can be a cationic derivative of thenon-guar galactomannan polymer, which is obtained by reaction betweenthe hydroxyl groups of the polygalactomannan polymer and reactivequaternary ammonium compounds. Suitable quaternary ammonium compoundsfor use in forming the cationic galactomannan polymer derivativesinclude those conforming to the general formulas 1-5, as defined above.

Cationic non-guar galactomannan polymer derivatives formed from thereagents described above are represented by the general formula 6:

wherein R is the gum. The cationic galactomannan derivative can be a gumhydroxypropyltrimethylammonium chloride, which can be more specificallyrepresented by the general formula 7:

Alternatively the galactomannan polymer derivative can be an amphotericgalactomannan polymer derivative having a net positive charge, obtainedwhen the cationic galactomannan polymer derivative further comprises ananionic group.

The cationic non-guar galactomannan can have a ratio of mannose togalactose is greater than about 4:1, a molecular weight of about 1,000g/mol to about 10,000,000 g/mol, and/or from about 50,000 g/mol to about1,000,000 g/mol, and/or from about 100,000 g/mol to about 900,000 g/mol,and/or from about 150,000 g/mol to about 400,000 g/mol and a cationiccharge density from about 1 meq/g to about 5 meq/g, and/or from 2 meq/gto about 4 meq/g and can be derived from a cassia plant.

The hair care compositions can comprise at least about 0.05% of agalactomannan polymer derivative by weight of the composition,alternatively from about 0.05% to about 2%, by weight of thecomposition, of a galactomannan polymer derivative.

The hair care compositions can comprise water-soluble cationicallymodified starch polymers. As used herein, the term “cationicallymodified starch” refers to a starch to which a cationic group is addedprior to degradation of the starch to a smaller molecular weight, orwherein a cationic group is added after modification of the starch toachieve a desired molecular weight. The definition of the term“cationically modified starch” also includes amphoterically modifiedstarch. The term “amphoterically modified starch” refers to a starchhydrolysate to which a cationic group and an anionic group are added.

The hair care compositions can comprise cationically modified starchpolymers at a range of about 0.01% to about 10%, and/or from about 0.05%to about 5%, by weight of the composition.

The cationically modified starch polymers disclosed herein have apercent of bound nitrogen of from about 0.5% to about 4%.

The cationically modified starch polymers for use in the hair carecompositions can have a molecular weight about 850,000 g/mol to about1,500,000 g/mol and/or from about 900,000 g/mol to about 1,500,000g/mol.

The hair care compositions can include cationically modified starchpolymers which have a charge density of from about 0.2 meq/g to about 5meq/g, and/or from about 0.2 meq/g to about 2 meq/g. The chemicalmodification to obtain such a charge density includes, but is notlimited to, the addition of amino and/or ammonium groups into the starchmolecules. Non-limiting examples of these ammonium groups may includesubstituents such as hydroxypropyl trimmonium chloride,trimethylhydroxypropyl ammonium chloride, dimethylstearylhydroxypropylammonium chloride, and dimethyldodecylhydroxypropyl ammonium chloride.See Solarek, D. B., Cationic Starches in Modified Starches: Propertiesand Uses, Wurzburg, 0. B., Ed., CRC Press, Inc., Boca Raton, Fla. 1986,pp 113-125. The cationic groups may be added to the starch prior todegradation to a smaller molecular weight or the cationic groups may beadded after such modification.

The cationically modified starch polymers generally have a degree ofsubstitution of a cationic group from about 0.2 to about 2.5. As usedherein, the “degree of substitution” of the cationically modified starchpolymers is an average measure of the number of hydroxyl groups on eachanhydroglucose unit which is derivatized by substituent groups. Sinceeach anhydroglucose unit has three potential hydroxyl groups availablefor substitution, the maximum possible degree of substitution is 3. Thedegree of substitution is expressed as the number of moles ofsubstituent groups per mole of anhydroglucose unit, on a molar averagebasis. The degree of substitution may be determined using proton nuclearmagnetic resonance spectroscopy (“.sup.1H NMR”) methods well known inthe art. Suitable.sup.1H NMR techniques include those described in“Observation on NMR Spectra of Starches in Dimethyl Sulfoxide,Iodine-Complexing, and Solvating in Water-Dimethyl Sulfoxide”, Qin-JiPeng and Arthur S. Perlin, Carbohydrate Research, 160 (1987), 57-72; and“An Approach to the Structural Analysis of Oligosaccharides by NMRSpectroscopy”, J. Howard Bradbury and J. Grant Collins, CarbohydrateResearch, 71, (1979), 15-25.

The source of starch before chemical modification can be chosen from avariety of sources such as tubers, legumes, cereal, and grains.Non-limiting examples of this source starch may include corn starch,wheat starch, rice starch, waxy corn starch, oat starch, cassava starch,waxy barley, waxy rice starch, glutenous rice starch, sweet rice starch,amioca, potato starch, tapioca starch, oat starch, sago starch, sweetrice, or mixtures thereof.

The cationically modified starch polymers can be selected from degradedcationic maize starch, cationic tapioca, cationic potato starch, andmixtures thereof. Alternatively, the cationically modified starchpolymers are cationic corn starch and cationic tapioca.

The starch, prior to degradation or after modification to a smallermolecular weight, may comprise one or more additional modifications. Forexample, these modifications may include cross-linking, stabilizationreactions, phosphorylations, and hydrolyzations. Stabilization reactionsmay include alkylation and esterification.

The cationically modified starch polymers may be incorporated into thecomposition in the form of hydrolyzed starch (e.g., acid, enzyme, oralkaline degradation), oxidized starch (e.g., peroxide, peracid,hypochlorite, alkaline, or any other oxidizing agent),physically/mechanically degraded starch (e.g., via the thermo-mechanicalenergy input of the processing equipment), or combinations thereof.

An optimal form of the starch is one which is readily soluble in waterand forms a substantially clear (% Transmittance of about 80 at 600 nm)solution in water. The transparency of the composition is measured byUltra-Violet/Visible (UV/VIS) spectrophotometry, which determines theabsorption or transmission of UV/VIS light by a sample, using a GretagMacbeth Colorimeter Color i 5 according to the related instructions. Alight wavelength of 600 nm has been shown to be adequate forcharacterizing the degree of clarity of cosmetic compositions.

Suitable cationically modified starch for use in hair care compositionsare available from known starch suppliers. Also suitable for use in haircare compositions are nonionic modified starch that can be furtherderivatized to a cationically modified starch as is known in the art.Other suitable modified starch starting materials may be quaternized, asis known in the art, to produce the cationically modified starch polymersuitable for use in hair care compositions.

Starch Degradation Procedure: a starch slurry can be prepared by mixinggranular starch in water. The temperature is raised to about 35° C. Anaqueous solution of potassium permanganate is then added at aconcentration of about 50 ppm based on starch. The pH is raised to about11.5 with sodium hydroxide and the slurry is stirred sufficiently toprevent settling of the starch. Then, about a 30% solution of hydrogenperoxide diluted in water is added to a level of about 1% of peroxidebased on starch. The pH of about 11.5 is then restored by addingadditional sodium hydroxide. The reaction is completed over about a 1 toabout 20 hour period. The mixture is then neutralized with dilutehydrochloric acid. The degraded starch is recovered by filtrationfollowed by washing and drying.

The hair care composition can comprise a cationic copolymer of anacrylamide monomer and a cationic monomer, wherein the copolymer has acharge density of from about 1.0 meq/g to about 3.0 meq/g. The cationiccopolymer can be a synthetic cationic copolymer of acrylamide monomersand cationic monomers.

The cationic copolymer can comprise:

-   -   (i) an acrylamide monomer of the following Formula AM:

-   -   where R⁹ is H or C₁₋₄ alkyl; and R¹⁰ and R¹¹ are independently        selected from the group consisting of H, C₁₋₄ alkyl, CH₂OCH₃,        CH₂OCH₂CH(CH₃)₂, and phenyl, or together are C₃₋₆cycloalkyl; and    -   (ii) a cationic monomer conforming to Formula CM:

where k=1, each of v, v′, and v″ is independently an integer of from 1to 6, w is zero or an integer of from 1 to 10, and X⁻ is an anion.

The cationic monomer can conform to Formula CM and where k=1, v=3 andw=0, z=1 and X⁻ is Cl⁻ to form the following structure:

The above structure may be referred to as diquat. Alternatively, thecationic monomer can conform to Formula CM and wherein v and v″ are each3, v′=1, w=1, y=1 and X⁻ is Cl⁻, such as:

The above structure may be referred to as triquat.

Suitable acrylamide monomer include, but are not limited to, eitheracrylamide or methacrylamide.

The cationic copolymer (b) can be AM:TRIQUAT which is a copolymer ofacrylamide and1,3-Propanediaminium,N-[2-[[[dimethyl[3-[(2-methyl-1-oxo-2-propenyl)amino]propyl]ammonio]acetyl]amino]ethyl]2-hydroxy-N,N,N′,N′,N′-pentamethyl-,trichloride. AM:TRIQUAT is also known as polyquaternium 76 (PQ76).AM:TRIQUAT may have a charge density of 1.6 meq/g and a molecular weightof 1.1 million g/mol.

In an alternative embodiment, the cationic copolymer is of an acrylamidemonomer and a cationic monomer, wherein the cationic monomer is selectedfrom the group consisting of: dimethylaminoethyl (meth)acrylate,dimethylaminopropyl (meth)acrylate, ditertiobutylaminoethyl(meth)acrylate, dimethylaminomethyl (meth)acrylamide,dimethylaminopropyl (meth)acrylamide; ethylenimine, vinylamine,2-vinylpyridine, 4-vinylpyridine; trimethylammonium ethyl (meth)acrylatechloride, trimethylammonium ethyl (meth)acrylate methyl sulphate,dimethylammonium ethyl (meth)acrylate benzyl chloride, 4-benzoylbenzyldimethylammonium ethyl acrylate chloride, trimethyl ammonium ethyl(meth)acrylamido chloride, trimethyl ammonium propyl (meth)acrylamidochloride, vinylbenzyl trimethyl ammonium chloride, diallyldimethylammonium chloride, and mixtures thereof.

The cationic copolymer can comprise a cationic monomer selected from thegroup consisting of: cationic monomers include trimethylammonium ethyl(meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methylsulphate, dimethylammonium ethyl (meth)acrylate benzyl chloride,4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamido chloride, trimethyl ammonium propyl(meth)acrylamido chloride, vinylbenzyl trimethyl ammonium chloride, andmixtures thereof.

The cationic copolymer can be water-soluble. The cationic copolymer isformed from (1) copolymers of (meth)acrylamide and cationic monomersbased on (meth)acrylamide, and/or hydrolysis-stable cationic monomers,(2) terpolymers of (meth)acrylamide, monomers based on cationic(meth)acrylic acid esters, and monomers based on (meth)acrylamide,and/or hydrolysis-stable cationic monomers. Monomers based on cationic(meth)acrylic acid esters may be cationized esters of the (meth)acrylicacid containing a quaternized N atom. In an embodiment, cationizedesters of the (meth)acrylic acid containing a quaternized N atom arequaternized dialkylaminoalkyl (meth)acrylates with C1 to C3 in the alkyland alkylene groups. Suitable cationized esters of the (meth)acrylicacid containing a quaternized N atom can be selected from the groupconsisting of: ammonium salts of dimethylaminomethyl (meth)acrylate,dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate,diethylaminomethyl (meth)acrylate, diethylaminoethyl (meth)acrylate; anddiethylaminopropyl (meth)acrylate quaternized with methyl chloride. Inan embodiment, the cationized esters of the (meth)acrylic acidcontaining a quaternized N atom is dimethylaminoethyl acrylate, which isquaternized with an alkyl halide, or with methyl chloride or benzylchloride or dimethyl sulfate (ADAME-Quat). the cationic monomer whenbased on (meth)acrylamides can be quaternizeddialkylaminoalkyl(meth)acrylamides with C1 to C3 in the alkyl andalkylene groups, or dimethylaminopropylacrylamide, which is quaternizedwith an alkyl halide, or methyl chloride or benzyl chloride or dimethylsulfate.

Suitable cationic monomer based on a (meth)acrylamide includequaternized dialkylaminoalkyl(meth)acrylamide with C1 to C3 in the alkyland alkylene groups. The cationic monomer based on a (meth)acrylamidecan be dimethylaminopropylacrylamide, which is quaternized with an alkylhalide, especially methyl chloride or benzyl chloride or dimethylsulfate.

The cationic monomer can be a hydrolysis-stable cationic monomer.Hydrolysis-stable cationic monomers can be, in addition to adialkylaminoalkyl(meth)acrylamide, all monomers that can be regarded asstable to the OECD hydrolysis test. The cationic monomer can behydrolysis-stable and the hydrolysis-stable cationic monomer can beselected from the group consisting of: diallyldimethylammonium chlorideand water-soluble, cationic styrene derivatives.

The cationic copolymer can be a terpolymer of acrylamide,2-trimethylammoniumethyl (meth)acrylate quaternized with methyl chloride(ADAME-Q) and 3-dimethylammoniumpropyl(meth)acrylamide quaternized withmethyl chloride (DIMAPA-Q). The cationic copolymer can be formed fromacrylamide and acrylamidopropyltrimethylammonium chloride, wherein theacrylamidopropyltrimethylammonium chloride has a charge density of fromabout 1.0 meq/g to about 3.0 meq/g.

The cationic copolymer can have a charge density of from about 1.1 meq/gto about 2.5 meq/g, or from about 1.1 meq/g to about 2.3 meq/g, or fromabout 1.2 meq/g to about 2.2 meq/g, or from about 1.2 meq/g to about 2.1meq/g, or from about 1.3 meq/g to about 2.0 meq/g, or from about 1.3meq/g to about 1.9 meq/g.

The cationic copolymer can have a molecular weight from about 100thousand g/mol to about 1.5 million g/mol, or from about 300 thousandg/mol to about 1.5 million g/mol, or from about 500 thousand g/mol toabout 1.5 million g/mol, or from about 700 thousand g/mol to about 1.0million g/mol, or from about 900 thousand g/mol to about 1.2 milliong/mol.

The cationic copolymer can be a trimethylammoniopropylmethacrylamidechloride-N-Acrylamide copolymer, which is also known as AM:MAPTAC.AM:MAPTAC may have a charge density of about 1.3 meq/g and a molecularweight of about 1.1 million g/mol. The cationic copolymer can beAM:ATPAC. AM:ATPAC can have a charge density of about 1.8 meq/g and amolecular weight of about 1.1 million g/mol.

(a) Cationic Synthetic Polymers

The hair care composition can comprise a cationic synthetic polymer thatmay be formed from

i) one or more cationic monomer units, and optionally

ii) one or more monomer units bearing a negative charge, and/or

iii) a nonionic monomer,

wherein the subsequent charge of the copolymer is positive. The ratio ofthe three types of monomers is given by “m”, “p” and “q” where “m” isthe number of cationic monomers, “p” is the number of monomers bearing anegative charge and “q” is the number of nonionic monomers

The cationic polymers can be water soluble or dispersible,non-crosslinked, and synthetic cationic polymers having the followingstructure:

where A, may be one or more of the following cationic moieties:

where @=amido, alkylamido, ester, ether, alkyl or alkylaryl;where Y=C1-C22 alkyl, alkoxy, alkylidene, alkyl or aryloxy;where ψ=C1-C22 alkyl, alkyloxy, alkyl aryl or alkyl aryloxy;where Z=C1-C22 alkyl, alkyloxy, aryl or aryloxy;where R1=H, C1-C4 linear or branched alkyl;where s=0 or 1, n=0 or 1;where T and R7=C1-C22 alkyl; andwhere X−=halogen, hydroxide, alkoxide, sulfate or alkylsulfate.

Where the monomer bearing a negative charge is defined by R2′=H, C1-C4linear or branched alkyl and R3 as:

where D=O, N, or S;where Q=NH2 or 0;where u=1-6;where t=0-1; andwhere J=oxygenated functional group containing the following elements P,S, C.

Where the nonionic monomer is defined by R2″=H, C1-C4 linear or branchedalkyl, R6=linear or branched alkyl, alkyl aryl, aryl oxy, alkyloxy,alkylaryl oxy and β is defined as

andwhere G′ and G″ are, independently of one another, O, S or N—H and L=0or 1.

Examples of cationic monomers include aminoalkyl (meth)acrylates,(meth)aminoalkyl (meth)acrylamides; monomers comprising at least onesecondary, tertiary or quaternary amine function, or a heterocyclicgroup containing a nitrogen atom, vinylamine or ethylenimine;diallyldialkyl ammonium salts; their mixtures, their salts, andmacromonomers deriving from therefrom.

Further examples of cationic monomers include dimethylaminoethyl(meth)acrylate, dimethylaminopropyl (meth)acrylate,ditertiobutylaminoethyl (meth)acrylate, dimethylaminomethyl(meth)acrylamide, dimethylaminopropyl (meth)acrylamide, ethylenimine,vinylamine, 2-vinylpyridine, 4-vinylpyridine, trimethylammonium ethyl(meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methylsulphate, dimethylammonium ethyl (meth)acrylate benzyl chloride,4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamido chloride, trimethyl ammonium propyl(meth)acrylamido chloride, vinylbenzyl trimethyl ammonium chloride,diallyldimethyl ammonium chloride.

Suitable cationic monomers include those which comprise a quaternaryammonium group of formula —NR₃ ⁺, wherein R, which is identical ordifferent, represents a hydrogen atom, an alkyl group comprising 1 to 10carbon atoms, or a benzyl group, optionally carrying a hydroxyl group,and comprise an anion (counter-ion). Examples of anions are halides suchas chlorides, bromides, sulphates, hydrosulphates, alkylsulphates (forexample comprising 1 to 6 carbon atoms), phosphates, citrates, formates,and acetates.

Suitable cationic monomers include trimethylammonium ethyl(meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methylsulphate, dimethylammonium ethyl (meth)acrylate benzyl chloride,4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamido chloride, trimethyl ammonium propyl(meth)acrylamido chloride, vinylbenzyl trimethyl ammonium chloride.

Additional suitable cationic monomers include trimethyl ammonium propyl(meth)acrylamido chloride.

Examples of monomers bearing a negative charge include alphaethylenically unsaturated monomers comprising a phosphate or phosphonategroup, alpha ethylenically unsaturated monocarboxylic acids,monoalkylesters of alpha ethylenically unsaturated dicarboxylic acids,monoalkylamides of alpha ethylenically unsaturated dicarboxylic acids,alpha ethylenically unsaturated compounds comprising a sulphonic acidgroup, and salts of alpha ethylenically unsaturated compounds comprisinga sulphonic acid group.

Suitable monomers with a negative charge include acrylic acid,methacrylic acid, vinyl sulphonic acid, salts of vinyl sulfonic acid,vinylbenzene sulphonic acid, salts of vinylbenzene sulphonic acid,alpha-acrylamidomethylpropanesulphonic acid, salts ofalpha-acrylamidomethylpropanesulphonic acid, 2-sulphoethyl methacrylate,salts of 2-sulphoethyl methacrylate, acrylamido-2-methylpropanesulphonicacid (AMPS), salts of acrylamido-2-methylpropanesulphonic acid, andstyrenesulphonate (SS).

Examples of nonionic monomers include vinyl acetate, amides of alphaethylenically unsaturated carboxylic acids, esters of an alphaethylenically unsaturated monocarboxylic acids with an hydrogenated orfluorinated alcohol, polyethylene oxide (meth)acrylate (i.e.polyethoxylated (meth)acrylic acid), monoalkylesters of alphaethylenically unsaturated dicarboxylic acids, monoalkylamides of alphaethylenically unsaturated dicarboxylic acids, vinyl nitriles, vinylamineamides, vinyl alcohol, vinyl pyrolidone, and vinyl aromatic compounds.

Suitable nonionic monomers include styrene, acrylamide, methacrylamide,acrylonitrile, methylacrylate, ethylacrylate, n-propylacrylate,n-butylacrylate, methylmethacrylate, ethylmethacrylate,n-propylmethacrylate, n-butylmethacrylate, 2-ethyl-hexyl acrylate,2-ethyl-hexyl methacrylate, 2-hydroxyethylacrylate and2-hydroxyethylmethacrylate.

The anionic counterion (X−) in association with the synthetic cationicpolymers may be any known counterion so long as the polymers remainsoluble or dispersible in water, in the hair care composition, or in acoacervate phase of the hair care composition, and so long as thecounterions are physically and chemically compatible with the essentialcomponents of the hair care composition or do not otherwise undulyimpair product performance, stability or aesthetics. Non limitingexamples of such counterions include halides (e.g., chlorine, fluorine,bromine, iodine), sulfate and methylsulfate.

The cationic polymer described herein can aid in providing damaged hair,particularly chemically treated hair, with a surrogate hydrophobicF-layer. The microscopically thin F-layer provides naturalweatherproofing, while helping to seal in moisture and prevent furtherdamage. Chemical treatments damage the hair cuticle and strip away itsprotective F-layer. As the F-layer is stripped away, the hair becomesincreasingly hydrophilic. It has been found that when lyotropic liquidcrystals are applied to chemically treated hair, the hair becomes morehydrophobic and more virgin-like, in both look and feel. Without beinglimited to any theory, it is believed that the lyotropic liquid crystalcomplex creates a hydrophobic layer or film, which coats the hair fibersand protects the hair, much like the natural F-layer protects the hair.The hydrophobic layer returns the hair to a generally virgin-like,healthier state. Lyotropic liquid crystals are formed by combining thesynthetic cationic polymers described herein with the aforementionedanionic detersive surfactant component of the hair care composition. Thesynthetic cationic polymer has a relatively high charge density. Itshould be noted that some synthetic polymers having a relatively highcationic charge density do not form lyotropic liquid crystals, primarilydue to their abnormal linear charge densities. Such synthetic cationicpolymers are described in WO 94/06403 to Reich et al. The syntheticpolymers described herein can be formulated in a stable hair carecomposition that provides improved conditioning performance, withrespect to damaged hair.

Cationic synthetic polymers that can form lyotropic liquid crystals havea cationic charge density of from about 2 meq/gm to about 7 meq/gm,and/or from about 3 meq/gm to about 7 meq/gm, and/or from about 4 meq/gmto about 7 meq/gm. In some embodiments, the cationic charge density isabout 6.2 meq/gm. The polymers also have a M. Wt. of from about 1,000 toabout 5,000,000, and/or from about 10,000 to about 1,500,000, and/orfrom about 100,000 to about 1,500,000.

In another embodiment of the invention cationic synthetic polymers thatprovide enhanced conditioning and deposition of benefit agents but donot necessarily form lyotropic liquid crystals have a cationic chargedensity of from about 0.7 meq/gm to about 7 meq/gm, and/or from about0.8 meq/gm to about 5 meq/gm, and/or from about 1.0 meq/gm to about 3meq/gm. The polymers also have a M. Wt. of from about 1,000 to about1,500,000, from about 10,000 to about 1,500,000, and from about 100,000to about 1,500,000.

Suitable cationic cellulose polymers are salts of hydroxyethyl cellulosereacted with trimethyl ammonium substituted epoxide, referred to in theindustry (CTFA) as Polyquaternium 10 and available from Dow/AmercholCorp. (Edison, N.J., USA) in their Polymer LR, JR, and KG series ofpolymers. Non-limiting examples include: JR-30M, KG-30M, JP, LR-400 andmixtures thereof. Other suitable types of cationic cellulose include thepolymeric quaternary ammonium salts of hydroxyethyl cellulose reactedwith lauryl dimethyl ammonium-substituted epoxide referred to in theindustry (CTFA) as Polyquaternium 24. These materials are available fromDow/Amerchol Corp. under the tradename Polymer LM-200. Other suitabletypes of cationic cellulose include the polymeric quaternary ammoniumsalts of hydroxyethyl cellulose reacted with lauryl dimethylammonium-substituted epoxide and trimethyl ammonium substituted epoxidereferred to in the industry (CTFA) as Polyquaternium 67. These materialsare available from Dow/Amerchol Corp. under the tradename SoftCATPolymer SL-5, SoftCAT Polymer SL-30, Polymer SL-60, Polymer SL-100,Polymer SK-L, Polymer SK-M, Polymer SK-MH, and Polymer SK-H.

The concentration of the cationic polymers ranges about 0.025% to about5%, from about 0.1% to about 3%, and/or from about 0.2% to about 1%, byweight of the hair care composition.

C. Viscosity Reducing Agents

In an embodiment, the hair care composition described herein maycomprise from about 0.1% to about 35%, alternatively from about 0.25% toabout 30%, and alternatively from about 0.5% to about 25% of a viscosityreducing agent, by weight of the hair care composition. Non-limitingexamples of suitable viscosity reducing agents include Class Amaterials, Class B materials, water miscible solvents, hydrotropes, andmixtures thereof.

The hair care composition described herein may have a liquid phaseviscosity of from about 1 centipoise to about 6,000 centipoise,alternatively from about 1 centipoise to about 4,500 centipoise,alternatively from about 1 centipoise to about 3,000 centipoise, andalternatively from about 5 centipoise to about 2,000 centipoise.

1. Class a Viscosity Reducing Agents

The Class A viscosity reducing agents may have a partition dispersioncoefficient of from about −3.1 to about −0.7, alternatively from about−3 to about −0.85, and alternatively from about −2.92 to about −0.92.The Class A viscosity reducing agents may have a partition dispersioncoefficient of from about −3 to about −1.9, alternatively from about−2.9 to about −2, wherein the one or more viscosity reducing agents hasat least 2 polar groups, or has 1 polar group and less than 5 acyclicsp³ hybridized carbon atoms that are connected to each other in acontiguous group. The Class A viscosity reducing agents may have apartition dispersion coefficient of from about −3 to about −1.9,alternatively from about −2.9 to about −2, wherein the one or moreviscosity reducing agents has 2 to 4 polar groups, or has 1 polar groupand 1 to 3 acyclic sp³ hybridized carbon atoms that are connected toeach other in a contiguous group. The Class A viscosity reducing agentsmay have a partition dispersion coefficient of from about −3 to about−1, alternatively from about −2.9 to about −2, wherein the one or moreviscosity reducing agents has 2 to 4 polar groups, or has 1 polar groupand 2 acyclic sp³ hybridized carbon atoms that are connected to eachother in a contiguous group. The Class A viscosity reducing agents mayprovide unexpected viscosity reduction when used in the hair carecomposition described herein.

The partition dispersion coefficient (PDC) is defined by the followingequation:

PDC=log P−0.3001*(□D)2+10.362*□D−93.251

wherein log P is the octanol water partitioning coefficient as computedby the Consensus algorithm implemented in ACD/Percepta version 14.02 byAdvanced Chemistry Development, Inc. (ACD/Labs, Toronto, Canada), andwherein □D is the Hansen solubility dispersion parameter in (MPa)1/2computed using Steven Abbott and Hiroshi Yamamoto's “HSPIP—HansenSolubility Parameters in Practice” program, 4th Edition, version 4.1.07.

The viscosity reducing agents may be organic compounds comprising 1polar group, alternatively at least 1 polar group, alternatively 2 to 4polar groups, and alternative alternatively at least 2 polar groups. Thepolar groups may be selected from the group consisting of alcohols,aldehydes, esters, lactones, coumarins, ethers, ketones, phenol, phenyl,oxides, alkenyl, alkynyl, and combinations thereof. The viscosityreducing agents may have a molecular weight of between 100 daltons and300 daltons, alternatively from about 125 daltons to about 300 daltons.Additionally, the viscosity reducing agents may have a water solubilityat between 23 and 25 degrees Celsius of from about 900 to 50,000 mg/L.

The viscosity reducing agents may be selected from the group consistingof raspberry ketone, triethyl citrate, 5-methyl-3-heptanone oxime,hydroxycitronellal, camphor gum, 2-isopropyl-5-methyl-2-hexenal,eucalyptol, 1,1-dimethoxyoctane, isobutyl hexanoate, dihyro isojasmonate, and combinations thereof. Alternatively, the viscosityreducing agents may be selected from the group consisting of raspberryketone, triethyl citrate, hydroxycitronellal, camphor gum, andcombinations thereof. Alternatively, the viscosity reducing agent may beselected from the group consisting of raspberry ketone, triethylcitrate, hydroxycitronellal, and combinations thereof.

2. Class B Viscosity Reducing Agents

The Class B viscosity reducing agents may have a partition dispersioncoefficient of from about 0.05 to about 5.1, alternatively from about0.08 to about 4.5, alternatively from about 0.09 to about 4.4,alternatively from about 0.05 to about 2.0, alternatively from about0.08 to about 1.8, alternatively from about 0.09 to about 1.7, andalternatively from about 0.095 to about 1.68. The Class B viscosityreducing agents may provide unexpected viscosity reduction when used inthe hair care composition described herein.

The partition dispersion coefficient (PDC) is defined by the followingequation:

PDC=log P−0.3001*(□D)²+10.362*□D−93.251

wherein log P is the octanol water partitioning coefficient as computedby the Consensus algorithm implemented in ACD/Percepta version 14.02 byAdvanced Chemistry Development, Inc. (ACD/Labs, Toronto, Canada), andwherein □D is the Hansen solubility dispersion parameter in (MPa)^(1/2)computed using Steven Abbott and Hiroshi Yamamoto's “HSPIP—HansenSolubility Parameters in Practice” program, 4^(th) Edition, version4.1.07.

The viscosity reducing agents may be organic compounds comprising 1polar group, alternatively at least 1 polar group, alternatively 2 to 4polar groups, and alternative alternatively at least 2 polar groups. Thepolar groups may be selected from the group consisting of alcohols,aldehydes, esters, lactones, coumarins, ethers, ketones, phenol, phenyl,oxides, alkenyl, alkynyl, and combinations thereof. The viscosityreducing agents may have a molecular weight of between 100 daltons and300 daltons, alternatively from about 125 daltons to about 300 daltons.Additionally, the viscosity reducing agents may have a water solubilityat between 23 and 25 degrees Celsius of from about 10 to 900 mg/L.

The Class B viscosity reducing agents may be selected from the groupconsisting of veloutone, isoamyl salicylate, gamma-terpinene, linalyliso butyrate, alpha-terpinene, limonene, dipentene, geranyl phenylacetate, iso propyl myristate, hexadecane, and combinations thereof.Alternatively, the Class B viscosity reducing agents may be selectedfrom the group consisting of veloutone, gamma-terpinene, linalyl isobutyrate, alpha-terpinene, limonene, dipentene, geranyl phenyl acetate,iso propyl myristate, hexadecane, and combinations thereof.Alternatively, the Class B viscosity reducing agents may be selectedfrom the group consisting of veloutone, isoamyl salicylate,gamma-terpinene, linalyl iso butyrate, alpha-terpinene, limonene,dipentene, geranyl phenyl acetate, and combinations thereof.

3. Water Miscible Solvents

The carrier useful in embodiments of the hair care composition includeswater and water solutions of lower alkyl alcohols, polyhydric alcohols,ketones having from 3 to 4 carbons atoms, C1-C6 esters of C1-C6alcohols, sulfoxides, amides, carbonate esters, ethoxylated andproposylated C1-C10 alcohols, lactones, pyrollidones, and mixturesthereof. Non-limited lower alkyl alcohol examples are monohydricalcohols having 1 to 6 carbons, such as ethanol and isopropanol.Non-limiting examples of polyhydric alcohols useful herein includepropylene glycol, dipropylene glycol, butylenes glycol, hexylene glycol,glycerin, propane diol and mixtures thereof.

In an embodiment of the present invention, the hair care composition maycomprise a hydrotrope/viscosity modifier which is an alkali metal orammonium salt of a lower alkyl benzene sulphonate such as sodium xylenesulphonate, sodium cumene sulphonate or sodium toluene sulphonate.

In a further embodiment of the present invention, the hair carecomposition may comprise silicone/PEG-8 silicone/PEG-9 silicone/PEG-nsilicone/silicone ether (n could be another integer), non-limitingexamples include PEGS-dimethicone A208) MW 855, PEG 8 Dimethicone D208MW 2706.

D. Propellant or Blowing Agent

The concentrated hair care composition described herein may comprisefrom about from about 1% to about 10% propellant or blowing agent,alternatively from about 2% to about 8% propellant, by weight of theconcentrated hair care composition.

The propellant or blowing agent may comprise one or more volatilematerials, which in a gaseous state, may carry the other components ofthe concentrated hair care composition in particulate or droplet form oras a foam. The propellant or blowing agent may have a boiling pointwithin the range of from about −45° C. to about 5° C. The propellant orblowing agent may be liquefied when packaged in convention aerosolcontainers under pressure. The rapid boiling of the propellant orblowing agent upon leaving the aerosol foam dispenser may aid in theatomization or foaming of the other components of the concentrated haircare composition.

Aerosol propellants or blowing agents which may be employed in theaerosol composition may include the chemically-inert hydrocarbons suchas propane, n-butane, isobutane, cyclopropane, and mixtures thereof, aswell as halogenated hydrocarbons such as dichlorodifluoromethane,1,1-dichloro-1,1,2,2-tetrafluoroethane,1-chloro-1,1-difluoro-2,2-trifluoroethane,1-chloro-1,1-difluoroethylene, 1,1-difluoroethane, dimethyl ether,monochlorodifluoromethane, trans-1,3,3,3-tetrafluoropropene, andmixtures thereof. The propellant or blowing agent may comprisehydrocarbons such as isobutane, propane, and butane—these materials maybe used for their low ozone reactivity and may be used as individualcomponents where their vapor pressures at 21.1° C. range from about 1.17Bar to about 7.45 Bar, alternatively from about 1.17 Bar to about 4.83Bar, and alternatively from about 2.14 Bar to about 3.79 Bar.

E. Scalp Health Agents

In an embodiment of the present invention, one or more scalp healthagent may be added to provide scalp benefits in addition to theanti-fungal/anti-dandruff efficacy provided by the surfactant solubleanti-dandruff agents. This group of materials is varied and provides awide range of benefits including moisturization, barrier improvement,anti-fungal, anti-microbial and anti-oxidant, anti-itch, and sensates,and additional anti-dandruff agents such as zinc pyrithione (ZPT) orselenium sulfide. Such scalp health agents include but are not limitedto: vitamin E and F, salicylic acid, niacinamide, caffeine, panthenol,zinc oxide, zinc carbonate, glycols, glycolic acid, PCA, PEGs,erythritol, glycerin, triclosan, lactates, hyaluronates, allantoin andother ureas, betaines, sorbitol, glutamates, xylitols, menthol, menthyllactate, iso cyclomone, benzyl alcohol, a compound comprising thefollowing structure:

-   -   R₁ is selected from H, alkyl, amino alkyl, alkoxy;    -   Q=H₂, O, —OR₁, —N(R₁)₂, —OPO(OR₁)_(x), —PO(OR₁)_(x), —P(OR₁)_(x)        where x=1-2;    -   V=NR₁, O, —OPO(OR₁)_(x), —PO(OR₁)_(x), —P(OR₁)_(x) where x=1-2;    -   W=H₂, O;    -   X, Y=independently selected from H, aryl, naphthyl for n=0;    -   X, Y=aliphatic CH₂ or aromatic CH for n≥1 and Z is selected from        aliphatic CH₂, aromatic CH, or heteroatom;    -   A=lower alkoxy, lower alkylthio, aryl, subsitituted aryl or        fused aryl; and    -   stereochemistry is variable at the positions marked*.        and natural extracts/oils including peppermint, spearmint,        argan, jojoba and aloe.

F. Optional Ingredients

In accordance with embodiments of the present invention, the hair carecomposition may further comprise one or more optional ingredients,including benefit agents Suitable benefit agents include, but are notlimited to conditioning agents, cationic polymers silicone emulsions,anti-dandruff agents, gel networks, chelating agents, and, natural oilssuch as sun flower oil or castor oil. Additional suitable optionalingredients include but are not limited to perfumes, perfumemicrocapsules, colorants, particles, anti-microbials, foam busters,anti-static agents, rheology modifiers and thickeners, suspensionmaterials and structurants, pH adjusting agents and buffers,preservatives, pearlescent agents, solvents, diluents, anti-oxidants,vitamins and combinations thereof.

Such optional ingredients should be physically and chemically compatiblewith the components of the composition, and should not otherwise undulyimpair product stability, aesthetics, or performance. The CTFA CosmeticIngredient Handbook, Tenth Edition (published by the Cosmetic, Toiletry,and Fragrance Association, Inc., Washington, D.C.) (2004) (hereinafter“CTFA”), describes a wide variety of nonlimiting materials that can beadded to the composition herein.

1. Conditioning Agents

The conditioning agent of the hair care compositions can be a siliconeconditioning agent. The silicone conditioning agent may comprisevolatile silicone, non-volatile silicone, or combinations thereof. Theconcentration of the silicone conditioning agent typically ranges fromabout 0.01% to about 10%, by weight of the composition, from about 0.1%to about 8%, from about 0.1% to about 5%, and/or from about 0.2% toabout 3%. Non-limiting examples of suitable silicone conditioningagents, and optional suspending agents for the silicone, are describedin U.S. Reissue Pat. No. 34,584, U.S. Pat. Nos. 5,104,646, and5,106,609, which descriptions are incorporated herein by reference.

The silicone conditioning agents for use in the compositions of thepresent invention can have a viscosity, as measured at 25° C., fromabout 20 to about 2,000,000 centistokes (“csk”), from about 1,000 toabout 1,800,000 csk, from about 10,000 to about 1,500,000 csk, and/orfrom about 20,000 to about 1,500,000 csk.

The dispersed silicone conditioning agent particles typically have avolume average particle diameter ranging from about 0.01 micrometer toabout 60 micrometer. For small particle application to hair, the volumeaverage particle diameters typically range from about 0.01 micrometer toabout 4 micrometer, from about 0.01 micrometer to about 2 micrometer,from about 0.01 micrometer to about 0.5 micrometer.

Additional material on silicones including sections discussing siliconefluids, gums, and resins, as well as manufacture of silicones, are foundin Encyclopedia of Polymer Science and Engineering, vol. 15, 2d ed., pp204-308, John Wiley & Sons, Inc. (1989), incorporated herein byreference.

Silicone emulsions suitable for use in the embodiments of the presentinvention include, but are not limited to, emulsions of insolublepolysiloxanes prepared in accordance with the descriptions provided inU.S. Pat. No. 6,316,541 or 4,476,282 or U.S. Patent ApplicationPublication No. 2007/0276087. Accordingly, suitable insolublepolysiloxanes include polysiloxanes such as alpha, omegahydroxy-terminated polysiloxanes or alpha, omega alkoxy-terminatedpolysiloxanes having an internal phase viscosity from about 5 csk toabout 500,000 csk. For example, the insoluble polysiloxane may have aninternal phase viscosity less 400,000 csk, preferably less than 200,000csk, more preferably from about 10,000 csk to about 180,000 csk. Theinsoluble polysiloxane can have an average particle size within therange from about 10 nm to about 10 micron. The average particle size maybe within the range from about 15 nm to about 5 micron, from about 20 nmto about 1 micron, or from about 25 nm to about 500 nm.

The average molecular weight of the insoluble polysiloxane, the internalphase viscosity of the insoluble polysiloxane, the viscosity of thesilicone emulsion, and the size of the particle comprising the insolublepolysiloxane are determined by methods commonly used by those skilled inthe art, such as the methods disclosed in Smith, A. L. The AnalyticalChemistry of Silicones, John Wiley & Sons, Inc.: New York, 1991. Forexample, the viscosity of the silicone emulsion can be measured at 30°C. with a Brookfield viscometer with spindle 6 at 2.5 rpm. The siliconeemulsion may further include an additional emulsifier together with theanionic surfactant,

Other classes of silicones suitable for use in compositions of thepresent invention include but are not limited to: i) silicone fluids,including but not limited to, silicone oils, which are flowablematerials having viscosity less than about 1,000,000 csk as measured at25° C.; ii) aminosilicones, which contain at least one primary,secondary or tertiary amine; iii) cationic silicones, which contain atleast one quaternary ammonium functional group; iv) silicone gums; whichinclude materials having viscosity greater or equal to 1,000,000 csk asmeasured at 25° C.; v) silicone resins, which include highlycross-linked polymeric siloxane systems; vi) high refractive indexsilicones, having refractive index of at least 1.46, and vii) mixturesthereof.

The conditioning agent of the hair care compositions of the presentinvention may also comprise at least one organic conditioning materialsuch as oil or wax, either alone or in combination with otherconditioning agents, such as the silicones described above. The organicmaterial can be non-polymeric, oligomeric or polymeric. It may be in theform of oil or wax and may be added in the formulation neat or in apre-emulsified form. Some non-limiting examples of organic conditioningmaterials include, but are not limited to: i) hydrocarbon oils; ii)polyolefins, iii) fatty esters, iv) fluorinated conditioning compounds,v) fatty alcohols, vi) alkyl glucosides and alkyl glucoside derivatives;vii) quaternary ammonium compounds; viii) polyethylene glycols andpolypropylene glycols having a molecular weight of up to about 2,000,000including those with CTFA names PEG-200, PEG-400, PEG-600, PEG-1000,PEG-2M, PEG-7M, PEG-14M, PEG-45M and mixtures thereof.

2. Emusifiers

A variety of anionic and nonionic emulsifiers can be used in the haircare composition of the present invention. The anionic and nonionicemulsifiers can be either monomeric or polymeric in nature. Monomericexamples include, by way of illustrating and not limitation, alkylethoxylates, alkyl sulfates, soaps, and fatty esters and theirderivatives. Polymeric examples include, by way of illustrating and notlimitation, polyacrylates, polyethylene glycols, and block copolymersand their derivatives. Naturally occurring emulsifiers such as lanolins,lecithin and lignin and their derivatives are also non-limiting examplesof useful emulsifiers.

3. Chelating Agents

The hair care composition can also comprise a chelant. Suitable chelantsinclude those listed in A E Martell & R M Smith, Critical StabilityConstants, Vol. 1, Plenum Press, New York & London (1974) and A EMartell & R D Hancock, Metal Complexes in Aqueous Solution, PlenumPress, New York & London (1996) both incorporated herein by reference.When related to chelants, the term “salts and derivatives thereof” meansthe salts and derivatives comprising the same functional structure(e.g., same chemical backbone) as the chelant they are referring to andthat have similar or better chelating properties. This term includealkali metal, alkaline earth, ammonium, substituted ammonium (i.e.monoethanolammonium, diethanolammonium, triethanolammonium) salts,esters of chelants having an acidic moiety and mixtures thereof, inparticular all sodium, potassium or ammonium salts. The term“derivatives” also includes “chelating surfactant” compounds, such asthose exemplified in U.S. Pat. No. 5,284,972, and large moleculescomprising one or more chelating groups having the same functionalstructure as the parent chelants, such as polymeric EDDS(ethylenediaminedisuccinic acid) disclosed in U.S. Pat. No. 5,747,440.

Levels of the EDDS chelant in the hair care compositions can be as lowas about 0.01 wt % or even as high as about 10 wt %, but above thehigher level (i.e., 10 wt %) formulation and/or human safety concernsmay arise. In an embodiment, the level of the EDDS chelant may be atleast about 0.05 wt %, at least about 0.1 wt %, at least about 0.25 wt%, at least about 0.5 wt %, at least about 1 wt %, or at least about 2wt % by weight of the hair care composition. Levels above about 4 wt %can be used but may not result in additional benefit.

4. Aqueous Carrier

The hair care compositions can be in the form of pourable liquids (underambient conditions). Such compositions will therefore typically comprisea carrier, which is present at a level of from about 40% to about 85%,alternatively from about 45% to about 80%, alternatively from about 50%to about 75% by weight of the hair care composition. The carrier maycomprise water, or a miscible mixture of water and organic solvent, andin one aspect may comprise water with minimal or no significantconcentrations of organic solvent, except as otherwise incidentallyincorporated into the composition as minor ingredients of otheressential or optional components.

The carrier useful in embodiments of the hair care compositions of thepresent invention includes water and water solutions of lower alkylalcohols and polyhydric alcohols. The lower alkyl alcohols useful hereinare monohydric alcohols having 1 to 6 carbons, in one aspect, ethanoland isopropanol. Exemplary polyhydric alcohols useful herein includepropylene glycol, hexylene glycol, glycerin, and propane diol.

G. Foam Dispenser

The hair care composition described herein may be provided in a foamdispenser. The foam dispenser may be an aerosol foam dispenser. Theaerosol foam dispenser may comprise a reservoir for holding the hairtreatment composition. The reservoir may be made out of any suitablematerial selected from the group consisting of plastic, metal, alloy,laminate, and combinations thereof. In an embodiment, the reservoir maybe for one-time use. In an embodiment, the reservoir may be removablefrom the aerosol foam dispenser. Alternatively, the reservoir may beintegrated with the aerosol foam dispenser. In an embodiment, there maybe two or more reservoirs.

The foam dispenser may also be a mechanical foam dispenser. Themechanical foam dispenser described may be selected from the groupconsisting of squeeze foam dispensers, pump foam dispensers, othermechanical foam dispensers, and combinations thereof. In an embodiment,the mechanical foam dispenser is a squeeze foam dispenser. Non-limitingexamples of suitable pump dispensers include those described in WO2004/078903, WO 2004/078901, and WO 2005/078063 and may be supplied byAlbea (60 Electric Ave., Thomaston, Conn. 06787 USA) or Rieke PackagingSystems (500 West Seventh St., Auburn, Ind. 46706).

The mechanical foam dispenser may comprise a reservoir for holding theconcentrated hair treatment composition. The reservoir may be made outof any suitable material selected from the group consisting of plastic,metal, alloy, laminate, and combinations thereof. The reservoir may be arefillable reservoir such as a pour-in or screw-on reservoir, or thereservoir may be for one-time use. The reservoir may also be removablefrom the mechanical foam dispenser. Alternatively, the reservoir may beintegrated with the mechanical foam dispenser. In an embodiment, theremay be two or more reservoirs.

In an embodiment, the reservoir may be comprised of a material selectedfrom the group consisting of rigid materials, flexible materials, andcombinations thereof. The reservoir may be comprised of a rigid materialif it does not collapse under external atmospheric pressure when it issubject to an interior partial vacuum.

H. Product Form

The hair care compositions of the present invention may be presented intypical hair care formulations. They may be in the form of solutions,dispersion, emulsions, powders, talcs, encapsulated, spheres, spongers,solid dosage forms, foams, and other delivery mechanisms. Thecompositions of the embodiments of the present invention may be hairtonics, leave-on hair products such as treatment, and styling products,rinse-off hair products such as shampoos and personal cleansingproducts, and treatment products; and any other form that may be appliedto hair.

I. Applicator

In an embodiment of the present invention, the hair care composition maybe dispensed from an applicator for dispensing directly to the scalparea. Dispensing directly onto the scalp via a targeted deliveryapplicator enables deposition of the non diluted cleaning agentsdirectly where the cleaning needs are highest. This also minimizes therisk of eye contact with the cleansing solution.

The applicator is attached or can be attached to a bottle containing thecleansing prodhair care composition. The applicator can consist of abase that holds or extends to a single or plurality of tines. The tineshave openings that may be at the tip, the base or at any point betweenthe tip and the base. These openings allows for the product to bedistributed from the bottle directly onto the hair and/or scalp.

Alternatively, the applicator can also consist of brush-like bristlesattached or extending from a base. In this case product would dispensefrom the base and the bristles would allow for product distribution viathe combing or brushing motion.

Applicator and tine design and materials can also be optimized to enablescalp massage. In this case it would be beneficial for the tine orbristle geometry at the tips to be more rounded similar to the rollerball applicator used for eye creams. It may also be beneficial formaterials to be smoother and softer; for example metal or metal-likefinishes, “rubbery materials”.

Viscosity Measurement

Shampoo viscosities can be measured on a 2.5 mL sample using a cone andplate Brookfield RS rheometer with cone C75-1 at 2 s⁻¹, 27° C. at 3mins.

Measurement of Diffusion Coefficients by NMR

Surfactant-soluble agent containing cleansing compositions are dilutedwith de-ionized water to a surfactant concentration of about 1.3%. Thisdilution factor is believed to be representative of a cleansingcomposition when applied to a head during use. The diluted samples areintroduced into 5 mm NMR tubes with no further preparation. Nodeuterated solvents are present, therefore all experiments are rununlocked. Diffusion coefficients are determined using vendor-suppliedpulse sequence (“ledbpgppr2s”, stimulated echo with bipolar gradients,longitudinal eddy current delay, presaturation and 2 spoil gradients)using a Bruker Avance 700 MHz NMR spectrometer equipped with a BB 0 zgradient probe. Gradient pulse durations ranged between 3000-6000 us,with diffusion periods set at 150 ms. 32 linearly-spaced gradient valuesare used ranging from 2%-95% of 10 A current from a GREAT 3/10amplifier, with resulting gradient strengths given by 5 Gauss/cm/A. Dataare processed using vendor supplied software.

The surfactant micelle diffusion coefficient is designated as D_(S) andthe surfactant-soluble agent diffusion coefficient is designated asD_(A). The ratio of the surfactant diffusion coefficient to thesurfactant-soluble agent diffusion coefficient can be calculated usingthe following equation:

${{Ratio}\mspace{14mu}{of}\mspace{14mu}{Diffusion}\mspace{14mu}{Coefficients}} = \frac{D_{S}}{D_{A}}$

Measurement of Surfactant-Soluble Agent Deposition

Surfactant-soluble agent deposition in-vivo on scalp can be determinedby ethanol extraction of the agent after the scalp has been treated witha surfactant-soluble agent containing cleansing composition and rinsedoff. The concentration of agent in the ethanol extraction solvent ismeasured by HPLC. Quantitation is made by reference to a standard curve.The concentration detected by HPLC is converted into an amount collectedin grams by using the concentration multiplied by volume.

The percent agent deposited can be calculated using the followingequation:

${\%\mspace{14mu}{agent}\mspace{14mu}{deposited}} = {\frac{\frac{{grams}\mspace{14mu}{of}\mspace{14mu}{agent}\mspace{14mu}{deposited}}{{area}\mspace{14mu}{of}\mspace{14mu}{scalp}\mspace{14mu}{extracted}}}{\frac{\left( {{{wt}.\%}\mspace{14mu}{agent}\mspace{14mu}{in}\mspace{14mu}{shampoo}} \right) \times \left( {{grams}\mspace{14mu}{of}\mspace{14mu}{shampoo}\mspace{14mu}{applied}} \right)}{{area}\mspace{14mu}{of}\mspace{14mu}{scalp}\mspace{14mu}{treated}}} \times 100\%}$

The deposition efficiency can be calculated using the followingequation:

$\begin{matrix}{{{Deposition}\mspace{14mu}{efficiency}} = \frac{\%\mspace{14mu}{agent}\mspace{14mu}{deposited}\mspace{14mu}{by}\mspace{14mu}{example}\mspace{14mu}{formula}}{\%\mspace{14mu}{agent}\mspace{14mu}{deposited}\mspace{14mu}{by}\mspace{14mu}{control}\mspace{14mu}{formula}}} & \;\end{matrix}$

Preparation of Shampoo Compositions

The shampoo compositions are prepared by adding surfactants,anti-dandruff agents, perfume, viscosity modifiers, cationic polymersand the remainder of the water with ample agitation to ensure ahomogenous mixture. The mixture can be heated to 50-75° C. to speed thesolubilization of the soluble agents, then cooled. Product pH may beadjusted as necessary to provide shampoo compositions of the presentinvention which are suitable for application to human hair and scalp,and may vary based on the selection of particular detersive surfactantsand/or other components.

Non-Limiting Examples

The shampoo compositions illustrated in the following examples areprepared by conventional formulation and mixing methods. All exemplifiedamounts are listed as weight percents on an active basis and excludeminor materials such as diluents, preservatives, color solutions,imagery ingredients, botanicals, and so forth, unless otherwisespecified. All percentages are based on weight unless otherwisespecified.

Examples, active wt % 1 Ingredient (control) 2 Water q.s. q.s. SodiumLaureth-1 Sulfate (SLE1S)¹ 14.00 — Sodium Undecyl Sulfate ² — 28.00Piroctone Olamine ³ 1.00 0.5 Sodium Chloride ⁴ Up to 2% Up to 2%Preservatives, pH adjusters Up to 1% Up to 1% Diffusion Coefficient ofSurfactant, 8.06E−11 1.96E−10 D_(S) (m²/s) Diffusion Coefficient ofSurfactant- 7.94E−11 1.02E−10 soluble agent, D_(A) (m²/s) Ratio ofDiffusion Coefficients, 1.0 1.9 D_(S)/D_(A) % Piroctone Olaminedeposited 1.3% 4.5% Deposition Efficiency (vs control) 1.0X 3.5X ¹SodiumUndecyl Sulfate at 70% active, supplier: P&G ² Sodium Laureth-1 Sulfateat 26% active, supplier: P&G ³ Octopirox, supplier: Clariant ⁴ SodiumChloride, supplier: Morton

Discussion of Results for Examples 1-2

For Example 1, the ratio of diffusion coefficients (D_(S)/D_(A)) isclose to 1.0 which indicates that the Piroctone Olamine is diffusing atthe same rate as the SLE1S micelles, implying that the Piroctone Olamineis within the SLE1S micelles. However, the ratio (D_(S)/D_(A)) forExample 2 is significantly greater than 1.0 which indicates that thePiroctone Olamine is diffusing at a different rate than the sodiumundecyl sulfate micelles, implying that the Piroctone Olamine is notwithin the sodium undecyl sulfate micelles. The implications of thePiroctone Olamine not being within the surfactant micelles in Example 2is reflected in the greatly increased deposition efficiency of Example 2which is 3.6× that of Example 1 (control).

Examples, active wt % 3 Ingredient (control) 4 Water q.s. q.s. SodiumLaureth-1 Sulfate¹ 14.00 8.00 Piroctone Olamine ² 1.00 1.00 SodiumChloride ³ Up to 2% Up to 2% Preservatives, pH adjusters Up to 1% Up to1% Viscosity (cps) 7300 1500 % Piractone Olamine deposited 0.91% 1.1%Deposition Efficiency (vs control) 1.0X 1.2X ¹Sodium Laureth-1 Sulfateat 26% active, supplier: P&G ² Octopirox, supplier: Clariant ³ SodiumChloride, supplier: Morton

Examples, active wt % 7 Ingredient (control) 8 Water q.s. q.s. SodiumLaureth-1 Sulfate¹ 14.00 14.00 Piroctone Olamine ² 1.00 1.00 SodiumChloride ³ Up to 2% 0.0 Preservatives, pH adjusters Up to 1% Up to 1%Viscosity (cps) 10300 <50 % Piractone Olamine deposited 1.3% 1.2%Deposition Efficiency (vs control) 1.0X 0.9X ¹Sodium Laureth-1 Sulfateat 26% active, supplier: P&G ² Octopirox, supplier: Clariant ³ SodiumChloride, supplier: Morton

Discussion of Results for Examples 3-8

Neither decreasing surfactant levels, such as in Examples 4 and 6, nordecreasing product viscosity, such as in Example 8, significantly impactdeposition efficiency versus their respective controls, Examples 3, 5,and 7. In fact Examples 4, 6, and 8 demonstrates deposition efficienciesranging 0.9-1.2× that of their respective controls.

Examples 9-13 below further exemplify embodiments of the presentinvention.

Examples, active wt % Ingredient 9 10 Water q.s. q.s. Sodium UndecylSulfate ¹ 28.00 28.00 Piroctone Olamine ² 0.5 0.5 Limonene ³ 7.00 —Linalyl Isobutyrate ⁴ — 7.00 Sodium Chloride ⁵ Up to 2% Up to 2%Preservatives, pH adjusters Up to 1% Up to 1% % Piractone Olaminedeposited 4.4% 4.2% Deposition Efficiency (vs control) 3.3X 3.2X ¹Sodium Undecyl Sulfate at 70% active, supplier: P&G ² Octopirox,supplier: Clariant ³ Limonene, supplier: Kerry ⁴ Linalyl Isobutyrate,supplier: Givaudan ⁵ Sodium Chloride, supplier: Morton

Examples, active wt % Ingredient 11 12 13 Water q.s. q.s. q.s. SodiumUndecyl Sulfate ¹ 24.00 28.00  24.00  Lauramidopropyl Betaine ² 4.00 —2.00 Piroctone Olamine ³ 0.5 1.00 1.00 Limonene ⁴ 7.00 7.00 7.00Polyquaternium-6 ⁵ 0.2 — 0.2  Guar Hydroxypropyltri- — 0.2  — moniumChloride ⁶ Polyquaternium-10 ⁷ — 0.2  — Sodium Chloride ⁸ Up to 1% Up to1% Up to 1% Fragrance — — 1.60 Preservatives, pH adjusters Up to 1% Upto 1% Up to 1% ¹ Sodium Undecyl Sulfate at 70% active, supplier: P&G ²Lauramidopropyl Betaine at 35% active, supplier: Solvay ³ Octopirox,supplier: Clariant ⁴ Limonene, supplier: Kerry ⁵ Mirapol 100 (40% activesolution), supplier: Solvay Novecare ⁶ Jaguar C-500, viscosity = 25-65cps, % Nitrogen = 1.15-1.45%, supplier: Solvay Novecare ⁷ UCARE PolymerJP, 2% soln viscosity = 30000, % Nitrogen = 0.8-1.1%, supplier: DowChemicals ⁸ Sodium Chloride, supplier: Morton

Microscopy Sample Preparation Method

10:1 dilution sample preparation: Weigh out 10.00±0.05 g of tap waterinto a glass vial. Add 1.00±0.02 g of shampoo to the tap water. Closevial cap tightly, and shake back and forth vigorously 20 times. Allowsample to sit for 5-24 hrs until milky phase has separated to the top.5:1 dilution sample preparation: Weigh out 10.00±0.05 g of tap waterinto a glass vial. Add 2.00±0.02 g of shampoo to the tap water. Closevial cap tightly, and shake back and forth vigorously 20 times. Allowsample to sit for 5-24 hrs until milky phase has separated to the top.

Microscope slide preparation: Use a 1 mL plastic bulb pipette to samplethe top milky phase of the dilution sample and place one drop onto amicroscopy slide, then place a glass microscope slide cover on top ofthe sample.

Dilution samples are evaluated under a 40× objective lens usingdifferential interference contrast (DIC) microscopy. Images are capturedby camera using imaging software AxioVs40 V 4.7.2.0 available from CarlZeiss Imaging Solutions.

Discussion of Results for Examples 11-13

Microscopy of dilutions of Examples 11, 12 & 13 show the presence oflimonene oil droplets trapped in coacervate. This is evidence that upondilution of the shampoo, both the coacervate and the limonene oil phaseseparate.

Examples, active wt % 14 Ingredient (control) 15 Water q.s. q.s. SodiumLaureth-1 Sulfate (SLE1S)¹ 14.00 — Sodium Undecyl Sulfate ² — 14.00Piroctone Olamine ³ 1.00 1.00 Sodium Chloride ⁴ Up to 2% Up to 2%Preservatives, pH adjusters Up to 1% Up to 1% Diffusion Coefficient ofSurfactant, 1.15E−10 1.78E−10 D_(S) (m²/s) Diffusion Coefficient ofSurfactant- 1.07E−10 1.18E−10 soluble agent, D_(A) (m²/s) Ratio ofDiffusion Coefficients, 1.1 1.5 D_(S)/D_(A) % Piroctone Olaminedeposited 1.1% 1.9% Deposition Efficiency (vs control) 1.0X 1.7X ¹SodiumLaureth-1 Sulfate at 26% active, supplier: P&G ² Sodium Undecyl Sulfateat 70% active, supplier: P&G ³ Octopirox, supplier: Clariant ⁴ SodiumChloride, supplier: Morton

Discussion of Results for Examples 14-15

For Example 14 (control), the ratio of diffusion coefficients(D_(S)/D_(A)) is close to 1.0 which indicates that the Piroctone Olamineis diffusing at the same rate as the SLE1S micelles, which allows one toinfer that the Piroctone Olamine is within the SLE1S micelle. However,in Example 15 where the SLE1S is replaced with Sodium Undecyl Sulfate,the ratio (D_(S)/D_(A)) is greater than 1.0. This change in D_(S)/D_(A)indicates that the Piroctone Olamine is diffusing at a different ratethan the Sodium Undecyl Sulfate micelles, which allows one to infer thatthe Piroctone Olamine is not within those micelles. The implication ofthe Piroctone Olamine not being within the surfactant micelles inExample 15 is reflected in the increased deposition efficiency ofExample 15 vs. Example 14 (control).

Examples, active wt % 16 Ingredient (control) 17 18 Water q.s. q.s. q.s.Sodium Laureth-1 Sulfate (SLE1S)¹ 14.00 — — Sodium Undecyl Sulfate ² —14.00 28.00 Climbazole ³ 1.00 1.00 2.00 Sodium Chloride ⁴ Up to 2% Up to2% Up to 2% Preservatives, pH adjusters Up to 1% Up to 1% Up to 1%Diffusion Coefficient of Surfactant, 8.50E−11 2.18E−10 2.05E−10 D_(S)(m²/s) Diffusion Coefficient of Surfactant 7.26E−11 9.83E−11 1.02E−10soluble agent, D_(A) (m²/s) Ratio of Diffusion Coefficients, 1.2 2.2 2.0D_(S)/D_(A) % Climbazole deposited 0.57% 1.1% 1.3% Deposition Efficiency(vs control) 1.0X 1.9X 2.5X ¹Sodium Laureth-1 Sulfate at 26% active,supplier: P&G ² Sodium Undecyl Sulfate at 70% active, supplier: P&G ³Climbazole, supplier: Symrise ⁴ Sodium Chloride, supplier: Morton

Discussion of Results for Examples 16-18

For Example 16 (control), the ratio of diffusion coefficients(D_(S)/D_(A)) is close to 1.0 which indicates that the Climbazole isdiffusing at the same rate as the SLE1S micelles, which allows one toinfer that the Climbazole is within the SLE1S micelle. However, inExample 17-18 where the SLE1S is replaced with Sodium Undecyl Sulfate,the ratio (D_(S)/D_(A)) is significantly greater than 1.0. This changein D_(S)/D_(A) indicates that the Climbazole is diffusing at a differentrate than the Sodium Undecyl Sulfate micelles, which allows one to inferthat the Climbazole is not within those micelles. Consequently, Examples17-18 are representative of the present invention and exhibitsignificantly greater deposition efficiency which is 1.9×-2.5× that ofExample 16 (control). This demonstrates that the present invention canbe broadly applied to a variety of soluble anti-dandruff agents.

Examples, active wt % 19 23 Ingredient (control) 20 21 22 (comparative)Water q.s. q.s. q.s. q.s. q.s. Sodium Laureth-1 Sulfate (SLE1S)¹ 14.0016.00 16.00 — 21.60 Sodium Trideceth-2 Sulfate ² — — — 16.00 — SodiumUndecyl Sulfate ³ — 8.00 — — 2.40 Sodium Decyl Sulfate ⁴ — — 8.00 8.00 —Piroctone Olamine ⁵ 1.00 2.00 2.00 2.00 2.00 Sodium Chloride ⁶ Up to 2%Up to 2% Up to 2% Up to 2% Up to 2% Preservatives, fragrance, pHadjusters Up to 2.5 Up to 2.5% Up to 2.5% Up to 2.5% Up to 2.5%Diffusion Coefficient of Surfactant, 1.10E−10 1.21E−10 1.55E−10 2.89E−101.21E−10 D_(S) (m²/s) Diffusion Coefficient of Surfactant- 9.05E−118.57E−11 1.07E−10 1.36E−10 1.03E−10 soluble agent, D_(A) (m²/s) Ratio ofDiffusion Coefficients, 1.2 1.4 1.4 2.1 1.2 D_(S)/D_(A) % PiroctoneOlamine deposited 2.1% 3.1% 3.0% 4.2% 2.4% Deposition Efficiency (vscontrol) 1.0X 1.5X 1.4X 2.0X 1.1X ¹Sodium Laureth-1 Sulfate at 26%active, supplier: P&G ² Sodium Trideceth-2 Sulfate at 65% active,supplier: Tianjin Tianzhi Fine Chemical Co ³ Sodium Undecyl Sulfate at70% active, supplier P&G ⁴ Sodium Decyl Sulfate at 70% active, supplier:P&G ⁵ Octopirox, supplier: Clariant ⁶ Sodium Chloride, supplier: Morton

Discussion of Results for Examples 19-23

This set of examples demonstrates that achieving diffusion coefficientratios (D_(S)/D_(A)) greater than 1.2 is key to achieving the desiredincreased deposition efficiencies. Examples 20-22 are representative ofthe present invention and demonstrate that it is possible to achievediffusion coefficient ratios (D_(S)/D_(A)) greater than 1.2 with avariety of surfactants. Consequently, Examples 20-22 exhibit greaterdeposition efficiencies (1.4-2.0×) than that of Example 19 (control).Example 23 is a comparative example and shows that even when a formulacontains Sodium Undecyl Sulfate, if D_(S)/D_(A) is close 1.0 thedeposition efficiency will be low and similar to that of the control(Example 19).

In the examples, all concentrations are listed as weight percent, unlessotherwise specified and may exclude minor materials such as diluents,filler, and so forth. The listed formulations, therefore, comprise thelisted components and any minor materials associated with suchcomponents. As is apparent to one of ordinary skill in the art, theselection of these minors will vary depending on the physical andchemical characteristics of the particular ingredients selected to makethe hair care composition.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A hair care composition comprising: a) from about14% to about 40% of one or more surfactants wherein one or more of thesurfactants is an anionic surfactant or combinations of anionicsurfactants wherein at least one of the surfactants has an alkyl chainof less than C12 or a branched alkyl chain and wherein a ratio ofsurfactants which are not anionic to surfactants that are anionic isless than or equal to about 0.2; b) from about 0.1% to 10% of one ormore surfactant soluble antidandruff agents; wherein when the hair carecomposition is diluted with de-ionized water to 1.3% surfactantconcentration has a ratio of surfactant diffusion coefficient to solubleagent diffusion coefficient of from 1.4 to 2.5 as measured by nuclearmagnetic resonance spectroscopy (NMR).
 2. A hair care compositionaccording to claim 1 further comprising an anionic surfactant selectedfrom the group consisting of anionic alkyl sulfates and alkyl ethersulfates having straight or branched alkyl chains and mixtures thereof.3. A hair care composition according to claim 1 further comprising ananionic surfactant selected from the group consisting of: a)R₁O(CH₂CHR₃O)_(y)SO₃M; b) CH₃(CH₂)_(z)CHR₂CH₂O(CH₂CHR₃O)_(y)SO₃M; and c)mixtures thereof, where R₁ represents CH₃(CH₂)₁₀, R₂ represents H or ahydrocarbon radical comprising 1 to 4 carbon atoms such that the sum ofthe carbon atoms in z and R₂ is 8, R₃ is H or CH₃, y is 0 to 7, theaverage value of y is about 1 when y is not zero (0), and M is amonovalent or divalent, positively-charged cation.
 4. A hair carecomposition according to claim 1 further comprising a surfactant orcombination of surfactants selected from the group consisting of sodiumlauryl sulfate, sodium laureth-n sulfate where n is between about 0.5 toabout 3.5, sodium C10-15 alkyl sulfate where the alkyl chain can belinear or branched, sodium C10-15 pareth-n sulfate where n is betweenabout 0.5 to about 3.5 and the alkyl chain can be linear or branched,sodium tridecyl sulfate, sodium trideceth-n sulfate where n is betweenabout 0.5 to about 3.5, an anionic surfactant selected from the groupconsisting of: a) R1O(CH2CHR3O)ySO3M; b)CH3(CH2)zCHR2CH2O(CH2CHR3O)ySO3M; and c) mixtures thereof, where R1represents CH3(CH2)10, R2 represents H or a hydrocarbon radicalcomprising 1 to 4 carbon atoms such that the sum of the carbon atoms inz and R2 is 8, R3 is H or CH3, y is 0 to 7, the average value of y isabout 1 when y is not zero (0), and M is a monovalent or divalent,positively-charged cation.
 5. A hair care composition according to claim1 further comprising a surfactant selected from the group consisting ofamphoteric, nonionic and zwitterionic surfactants and mixtures thereof.6. A hair care composition according to claim 1 wherein the surfactantsoluble agent is a hydroxyl pyridone.
 7. A hair care compositionaccording to claim 6 wherein the hydroxyl pyridone is piroctone olamine.8. A hair care composition according to claim 1 wherein the surfactantsoluble agent is an azole.
 9. A hair care composition according to claim8 wherein the azole is climbazole.
 10. A hair care composition accordingto claim 1 wherein the composition further comprising a cationicpolymer.
 11. A hair care composition according to claim 1 wherein thecomposition further comprising a conditioning agent.
 12. A hair carecomposition according to claim 11 wherein the conditioning agent is asilicone.
 13. A hair care composition according to claim 1 furthercomprising one or more scalp health agent.
 14. A hair care compositionaccording to claim 13 wherein the scalp health agent is zinc pyrithione.15. A hair care composition according to claim 13 wherein the scalphealth agent is salicylic acid.
 16. A hair care composition according toclaim 13 wherein the scalp health agent is menthol and/or menthyllactate.
 17. A hair care composition according to claim 1 furthercomprising from about 1% to about 7% of a perfume.
 18. A hair carecomposition according to claim 1 wherein the hair care composition isdispensed as a foam.
 19. A hair care composition according to claim 18wherein the hair care composition is dispensed as an aerosol foam.
 20. Ahair care composition according to claim 19 wherein a propellant or ablowing agent to dispense the composition as an aerosol foam is achemically inert hydrocarbon, a halogenated hydrocarbon, and mixturesthereof.
 21. A hair care composition according to claim 18 wherein thehair care composition is dispensed as a pumped foam.
 22. A hair carecomposition according to claim 1 wherein the hair care composition isapplied using an applicator.